The hydrgen Bonding and proton transfer between 4-amin-2-methyl-6-xabenz(f)is-quiolin-5rone (1) and acetic acid were discussed in detailo When (1) was recrystallized fromacetic acid white needles (4) were Qbtained, The elementalanalysis, DTA ana TGA of (4) gave that acetic acid vvas linked by hydrogen bond to e(1) in a 1:1 molar ratio, ln this case, the presence of hydrogen bonding between the amino group of (1) and the carbonyl group of acetic acid was found by means of IR spectra. From the UV spectral data it may be concluded that the hydroxy group of acetic acid is also bonded tb nitrogen atem of isoquinoline, since the enthalpy change of hydrogen bond formation between 4-amino-6-oxabenz(f)isoquinolin-5-one derivative and carboxylic acid is about 13kca1/mo1 in a non-polar so1vent. The results of fluorescence spectra revealed that ion pair was formed by proton transfer from the hydroxy group acetic acid to nitrogen atom of isoquinoline in the lowest excited state. ln addition, (4) fiuoresced very intensely in this state.

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The crystal structure of double metal oxide, Cu3TiOg, which containscupric and cuprous ions, has been studied by means of the single crystal X-ray diffraction analysis. Cu3TiO4 is obtained by heating the powder mixture with mixing ratio of Cu20:CuO:TiOa=1:1:1in aplatinum crucible at 1050Cin air. Since CusTiois dec mposed toCuO and TiO2 in the temperature range 600-900C, the reaction product needs tobe cooled rapidly.
The crystal is hexagonal with space group P63/mmc There is one formula unit in the unit cell of dimensiQns:ao=3.04A, cC=11.46A.h this structure, cupric and titanic ions are distributed randomly on the equivalent pQsitions which surrounded octahedrally by six oxygen-neig ibours. Eachcuprous ion has twooxygen neighbours disposed in a straight li:ne. The proposed rational formu1 of this compound is Cu2 (Cu2 Tio)

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Lead titanates of types Pbi.xTiOs.x and Pbi-xNavTiOs-x+(vi2) were prepared by selid-solid reaction among PbOTiO and Na3CO3, with Pb/Ti mol ratiobe1ow unity Above chemical formuiae were proved to bg reasonable on a basis of the fact that mixed reqctapts with TiQ2 in excess gave rise to mondphasic preovskitesby firing. Tetragonality of the defect crystals was traced as a function of temperature, indicating that the tetragonality or tetragonal strain considerably varied with the value x, whereas the Curie temperature was maintained approximatelyconstant. The latter fact was interpreted in terms of the possible occurrence offluctuation of compositions in the defect crystals. Dielectric constants at 1 MHz of palletized specimens of type PbixNayTiOs-x+(y/2) were measured as a function of temperature. Their profiles of e vs. T were characterized by diffused nature of e in the vicinity of Curie temperatures. The diffused nature was interpreted with a model in which microregions of a defect crystal have different compositions and therefore, different Curie points.

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Effects of ball-milling en the reaction of equimolar mixtures of BaCOs and SiO2 have been studied in the temperature range between 800 and 900C by means of isothermal thermogravimetry, electron microscopy, X-ray diffraction analysis and DTA.
The main part of the reaction, which corresponds to the formation of Ba2SiOi, was best expressed by Jander's equation and the activation energywas.determined as 53 kcal/mol irrespective of the ball-milling tirne. The reaction was found to proceed in three stages:
BaCOs+SiO2= BaSiOs+CO, (1)
BaCO3 +BaSiO3 = Ba2SiO4 + CO2 (2)
Ba2SiO+SiO2=2BaSiO3 (3)
The reaction (1) was independent of CO2 partial pressure, whereas the reaction (2) was checked by CO2.The increase in the reactivity as caused by ball-milling was detected by an endothermic peak at about 7500C in DTA. This peak was found to be associated with theformation of BaSiO3 (reaction(1)).The effect of ball-milling is possibly interpreted in terms of the decrease in particle size of BaCOs in early stage of ball-milling, and of the improvement of SiO2 dispersion in later stage, respectively.

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The effective distribution coeMcient in zone melting operation depends on such factors as zone travel rate, stirring of the melt-zone and entrapping of melted liquid in grown-up crystals. Part of melted liquid is occluded, when dentrites project from the solid-liquid interface. This occulusion decreases the separation effect in zone melting.
In this work the ratio of occlusion was estimated in order to find a relation between the effective distribution coeMcient and the factors mentioned above.
Samples used were naphthalene containing about 3 wt f5e of B-naphthol (k1) and phenol containing m cresol (1k). A glass tube of 18 mm 1. D. and 240 mm in packed length was used as a container. The melt-zone was stirred by a device equipped with an electromagnet and a rotor The zone travel rate(V)was fixed at 20, 40, 60, 80 and 100mm/hr, and the stirring rate was varried in a range of ON200 rpm at each zone travel rate.
The concentration profiles after single zone pass shewed effeetiveness of stirring (Figs. 1, 2 and 3). The effective distribution coeMeient (k) was expressed by the following equation

where p is the ratio of occlusion, r is the stirring rate and a is a constant. The effectivedistribution coeMcients estimated by the equation above were in good agreement with the experimental results (Tables 1 and 2).

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For the purpose confirming the applicability of the pore structure model 1) to the mass transfer process in porous media, we have measured the e ective diffusion coe cient D, of He, Ar and N2 gases through a commercial alumina catalyst, Neobeed C-5, having the pere structure of simple cubic lattice type (SC). The diffusion was regarded as mainly volumetric, since the effective diffusion coefficient was inversely proportional to the root of molecular weight (Table1). The ratio D, ID, i. e. Oe/L, where D is the diffusion coefficient in the pore and Oe/L is the ratio of opening fraction to tortuosity fraction, was determined experimentally to be O.12 as shown in Table 2, I espective of the pretreating temperature in the range of 450-1200 C and the kind of the gases used. This observed ratio was almost identical with the calculated value of Oe/L for the SC type
These results prove the propriety of the packing model of spherical elementary particle in porous body.

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DPPH, radical scavenger, was found to catalyze the polymerization of butyraldehyde under high pressure. The resulting polymer has polyacetal structure and depolymerizes t6 original monomer at the normal condition. The bulk polymerization of this monomer by DPPH cathlyst was studied at 5600-8240 kg/cm2 and 7-34oC, This polymerization reaction has a saturation yield wbich depends on the reaction pressure and temperature. The ceiling temperature derived from the extrapolation to zero yield on the plots of the saturation yield vs. temperature at the constant pressure increases with the pressure as giving 12 at 5500kg/cm2 and36 at 8240 kg/cm2.
The thermodynamic quantities accompanying the polymerization were estimated from the Clausiu.s-Clapeyron equation, measuring dV, volume change accempanying the polymerizatiori and using the pressure coeflicient of the ceiling temperature, The heat of polymerization, H, was-63 kcal/mol at 7000 kg/cm2 and the corresponding entropy chenge, Sp*, was -21 e.u.
Extrapolation to atmospheric pressure gives a ceiling temperature of -53 C, JHe*=-4.2kcal/mol and tSo =-19 e.u.

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Oxidative dehydrogenationof cumeneover heat-stable polyarylenequinone catalyst prepared by the reaction of diazotized benzidine with ben.zoquinone has been studied in gas phase using a xed bed reactor The experime:nts covered the ra:nges of temperature from 200 to350 C, and of contact time(VV/F)from 6 to229-cat hr/mo1 at atmospheric pressure. The reaction proceeded catalytically in air, main product from being ev-methylstyrene. Small amounts of-acetophenone and carbon dioxide were also formed. It is suggested from the reactionof isopropyI alcohol that the active site cf poIyaryIenequinone catalyst forox dative dehydrogenat 0 reaChOn IS qU none StrUcture,

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Catalytic activity of MgO-CaO-A120s-NiO for cracking of petroleum was gradually decreased when petroleum of some kinds was used.
As a result of X-ray and chemical analysis of that catalyst whose activity had been decreased, alarge amount of V205 an.d newly produced minera s were recognized.
In order to investigate the cause of decreasing activity, further studies on chemical composition of these new minerals considered to result from V20s, was carried out.
The chemical compositions of two minerals are as follows:
1) 3MgO.V20s, Orthorohombic system, lattice censtant a=8.32, b=11.43, c=6.05
2) 3(Ca, Mg)O.V20s, Hexagenal system, lattice cerstaftt a=10.365, c=37.058
It may be possible that these minerals produced in the catalyst form solid solution with the c ositions of 3(Mg..xNix)O, V205 and 3(Ca, Mgi-ptNix)O, 2 V, O, by replacing a part of MgO in these minerals with NiO.

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A photosensitive polymer with pendant cinnamic ester groups was prepared by the radical cepolymerization of vinyloxyethyl cinnamate(VEC) with maleicanhydride(MAH),
The polymer obtained from the equimelecular copolymerizationof VEC and MAH in ethyl methyl ketone(MEK) with the initiation of azobisisobutyronitrile was the alternative copolymer. The ratio of monomer reactivity VEC(Mi) and (M2) was also determined in MEK at 70CC; the value obtained was ri=O.21, r2=O.14, respectively.
The relative photosensitivities of copolymers containing5 wt% of sersitizer such as 5-nitroacenaphteRe, p-nitreakiline, N-acetyl-p-nitroaniline and N-acetyl-4-nitro-1-naphtylamine were 200, 281, 281, and 790, respectively. The reaction product of copolymer reacted with 4-nitre-1-naphtylamine, gave the same degree of relative photosensitivity as KPR.

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In an attempt to apply surface activity of mechanochemicai dehydrate to catalytic property, the behavior of gibbsite-hydrous silica mixture during mechanical grinding were investigated.
Gibbsite, Al(OH), , and hydrous silica, SiO2.n H20, were mixed in the ratio 10/90 (SiO2/AlxO3) and ground. r-A1203 of imperfect spinel structure and amorphous silica were formed by mechanochemical dehydration, and a considerable amount of solid acidity appeared on th surface through substitutiort (AIS eSi) between both particles. However, the acidity was not developed strongly (the highest value was O.2mrnol/g) because of the growth of secondary particles by aggregation and the adsorption of water from atmosphereoccurred during further grinding, Whereas, when the adsorped surface was cleanedup by heating, the amount of acidity in the range of high temperature from 800 to 1000 C was increased rapidly (the highest yalue was O.9mmol/g) and became almost equal to that ef commercial silica-alumina catalyst having same composition.On the other hand, when the mixture was ground in vacuum- to prevent the adsorption of water, ev-A120s was formed rapidly by accerelation of mechaRochemical dehydration.
It was suggested that the rapid increase in acidity was caused by elevatihg thermal stability of r-A1203 in high temperature ranges.

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The oxidation reaction of chromite by molten sodium salts was studied in the temperature range of 270N3500C. The grain size of chromite ores were kept constant through-out the reaction period, and the kinetic curves were analysed in consideration of the core-model. The rate of reaction was well expressed bythe following equatien:
1-(1-x)1/3 = kt
Where x was degree of oxidation ofCr20s, k was constant, t was reaction time.
The apparent activation energywas found to be about 30 kcal/mol for Transvaal, lndian and Brazilian chromite.
By the experimental results, the oxidation mechanism of chromite by molten sodium salts was assumed that the chromite was attacked by NaOH to form active Cr203 compound, which was then oxidized to chromate by NaNOs in the molten salts, and that the chemical reaction on the surface of unreacted core was the rate-determining step of the reaction.

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Liquid compound fertilizers containing cendensed phosphates have an ability to keep several heavy metals as trace elements in their solutions. In order to investigate the above character, the behavior of Mna2+ ien in the solution of ammonium condensed phosphates of short chain lengths has been studied mainly by using polarography and paper chromatography, Especially, differences of formation meehanism, stable zones, compositions of complex ion and precipitate of manganese among ertho-, pyro- and tripelyphosphate were investigated. The resultsobtained are summarized as follows:
In ammonium pyrophosphate solution, most of Mn2+ ion was precipitated in the same way as orthophosphate, but a small amount of the ion was kept as eomplex ion [Mn(P207)2]6- in the solution whose mole ratio of Mn2+/P205 was below O.5. The crystal phases precipitated in the solutions whose mole ratio being below and above 1.5 were different, and both were indicated by the same compesition expressed by (NH4)2Mng(P207)2.n H20 but n was different.
In the case of ammonium tripolyphosphate, the solubility of Mn2+ was large. Mn2+ ion was kept as complex ion [MnPsO10]3- in the solution of mole ratiobelow O.67 according to the formula (1), whereas the complex was decomposed and precipitated as NH4Mn2P3O10 n H2O in the solution of mole ratio above O.65 according to the formula (2).
Mn2+P30105- [MnP3O10] 3- (1)
[MnP3O10] 3-+Mn2+ NH M 2P801 H20 (2)

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Thermodynamic ion-association constants of hexaamminechromium(III) and tris(ethylenediamine) chromium(III)with iodide and perchlorate ions in aqueous solutions were determined by the conductometric and spectrophotometric methods. The values obtained by the conductometric method (Kcon) and the those by the spectrophotometric method (Ksp) at 25.00C are as follows:
Kcon=19 4, Ksp= 22 7for[Cr(NH3)6]3+-I- Kcon=26 6,
Ksp=21 4 for[Cr(en)3]3+-I-, Kcon=15 3 for[Cr(NH3)6]3+-CI04-,
Kcon=11 4 for[Cr(en)3]3+-CIO4-
Although no change was observed in the absorption spectra in ultra-violet region of these complexes in thepresence of perchlorate ions at higher concentration, the ion-asseciation constants of complex ions with perchlorate ions could be indirectly calculated from theapparent ion-association constants of cemplex ions with iodide ions determined in the solutions containing both iodide and perchlorate ions Ksp=16 4 for[Cr(en)8]3+-CIO4- and 10 8 for[Cr(NH3)6]3+- CI04-.
Though detailed comparison of constants determined by different methods was limited, it would be concluded that the ion-association constants obtained by conductometric method were in a relatively good agreement with those by spectrophotometric method. The ion-associationconstants for [Cr(NHs)G]3+-X- X=I, CIO4 would slightly be less than those for [Co(NH3)6]3+- X- which have been reported.

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The present paper deals with a method of determination of mercury inhot spring waters by flameless atomic absorption spectrophotometry. Further, themercury content and the chemical behavior of the elementary mercury in hot spring are described. Sulfide and iodide ions interfered the.determination of mercuryby the reduction-vapor phase technique. These interferences could, however, be minimized by the addition of potassium permanganate.
Waters collected from 55 hot springs were found to contain up to 26.O ppb mercury. High concentration of mercury have been found in waters from Shimoburo Springs, Aomori (10.0ppb), Osorezan Springs, Aomori (1.3 18.8 ppb), Gosyogake Springs, Akita (26.Oppb), Manza Springs, Gunma (O.30 19.5 ppb) and Kusatu Springs, Gunma (1.70N4.50 ppb). These hot springs' were acid waters containing relatively high quantity of chloride or sulfate.

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Carbon-13 NMR spectra of metal 2-thenoyltrifiuoroacetonates (M(TTA)., M=Mg, Ca, Sr, Ba, Zn, Cd, Pb, Al, Ga, ln) and 2-thenoyltrifluoroacetone (TTA) have been observed at 25.2 MHz. The resonance lines were assigned on basis of 1)the relative signal intensity, 2) the chemical shift and spin eoupling constant of homologous eompounds, 3) off-resonance decoupling techniq ue.
The values of iSC chemical shifts of TTA and M(TTA)n were given Table 1 and 3, respectiveiy.13C chemical shifts of C-1 and C-3 carbon on chelate ring in M(TTA)n had a correlation with electronegativity of metal bonded to the chelates. 13C resonance peak of C-1 and C-3 carbon shifted to lower magnetic field with increasing electronegativity as shewn in Fig.3. 13C chemical shifts of C-2 carbon on chelate ring was found tocorrelate with chemical shifts of proton bonded to C-2 carbon as shown in Fig. 7. 13C chemical shifts of C-2 carbon were also had a correlation withionic radius of the metal. 13C peak of C-2 carbon shifted to higher magnetic field with increasing ionic radius as shown in Fig. 6.
The coupling constants between carbon-13 and fiuorine were correlated with ionic radius or electronegativity of the metal. Coupling constant Ji3c-F increased with increasing ionic radius, while J13c c F decreased with increasing ionic radius as shown in Fig. 10.

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The interactien between cyclohexadienylide ion and alkali metal ionsor alkaline-earth metal methoxide ions in Meisenheimer complex or Meisenheimer-like complex was comected with the coplanarity or nitro group on the cyclohexadienylide ring and the degree of delocalization of rr electrens in cyclohexadienylide ring,
As a result of the measurement of the reaction rates, IR spectra, NMR spectra and dielectric constants, the following conclusions were obtalned concerning the relation between the stability and the structure of cemplexes,
(1) The stability of the cemplexes depends on the number of NO2 groups and the electric charge of the cation i. e, Li+ Na+ Rb+ Cs+ K+ and Ca+OCH3 Sr+OCH3 Ba+ocH3.
(2)Different lR spectra are observed for the ketal and C OR bons ofthe complexes with different cations.
(3) As the stability of the complexdecreases, the intensity of the IR absorptions of NO2 group becomes strong, and the absorptions of NO2 group disappear for the stable complex,
(4) Wave numbers of v asym and p sym of NO2 group of the cemplex shift toward to those of final preduet as the complex becomes unstable.

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lrradiation of a solution of an alkene (cyclohexene, tetramethylethylene, propene, bicyclo[2.2.1]hept-2-ene, bicyclo[2. 2. 1]hepta-2, 5-diene) and methyl phenylpropiolate or phenylethynyl methyl ketone in cyclehexane or acetonitril with a low pressure mercury lamp gave a cyclobutene derivative as a primary photoproduct, The structure of the cyclobutene derivative obtained from the reaction of bicyclo[2. 2. 1]hept-2-ene or bicyclo[2. 2, 1]hepta-2, 5-diene was confirmed to be exo-isorner by the comparison with the corresponding authentic specimen.The addition of methyl phenylpropiolate to propene showed regioselectivity. An oxetane derivative and a homo-Diels-Alder adduct were also formed in the reaction of phenylethynyl methyl ketone with bicyclo[2. 2. 1]hepta-2, 5-diene. The stereochemical assignment of exetane derivative was carried out by nmr spectroscopy and the mechanism of the product formation was alsobriefly discussed. Irradiation of: ethyl cinnamate or benzalacetone with an alklen, e (cyclohexene, bicyclo[2. 2. 1]hepta-2, 5-diene) under the similar reaction condition did net give any products but resulted in cis-trans isomerization of methyl cianamate or benzalacetene.

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The -radiation-induced radical addition reactions of such alcohols as CH30H, C2H50H, n- C3H70H and i-C3H70H to such polyflorocyclobutenes as(CF2)2CH=CCI(1), (CF2)2CF=CCI (2)and(CF2)2CH=CF(3)were studied.
In the case of (1)and(2), the attack of the -hydroxyalkyl radicals to the cyclobutenes occurred exclusively on the=CH or CF of the unsymmetrical double bond, yielding the corresponding 1:1 adducts. While, in the case of(3), the radicals attacked on either the =CHor =CF, yielding the two isomers, (CF2)2CH2CFCRR/OH(7)and(CF2)2CHFCHCRR' OH(8).
The ratio of the two isomers varied markedly with the structure of the alcohols, and this was attributed to the steric effect of alkyl groups of the alcohols.

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The -radiation-induced radical addition reactions of several aldehydes, CH3CHO, C2H5CHO, n-C3H7CHO and i-C3H7CHO to 1, 3, 3, 4, 4-pentaflorocyclobutene (1) were studied.
In the addition of aldehydes to (1), the acyl radical attacked both the =CF side and =CH side of the unsymmectrical double bond, yielding the two isomers, (CF2)2CH2CFCOR (4) and (CF2)2CHFCHCOR (5).The unsaturated 1:1 adduct, (CF2)2CH=CCOR (6) and the 1:2 adduct, ROCCH(CF2)2CHCOR(7) were also produced along with the 1:1 adducts.
The 1:1 adducts, (4) and (5) were obtained in a ratio of 1:2 independent of the structure of the aldehydes.
Although the adduct (5) was dehydrofluorinated upon standing at room temperature to yield the unsaturated adduct (6), the adduct (4) remained unchanged under the same condition.
The order in apparent reactivity of aldehydes observed in the addition reaction was as follows:

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The nitration of some 1, 3, 5-triazine derivatives substitued with anilino and phenyl groups was carried out with sulfuric acid and potassium nitrate as the nitrating reagent. The structures of the nitration products were confirmed by the direct comparison with the aUthentic samples or by NMR spectra. 2-Amino-4-(p-nitroanilino)- and -4-(2, 4-dinitroanilino)-1, 3, 5-triazines were obtained by the nitration of 2-amino-4-anilino-1, 3, 5-triazine. The analogous nitrocompounds were obtained by the nitration ef 2-amino-4-anilino-6-methyl-1, 3, 5-triaziRe. 2, 4-Diamino-6-(m-nitrophenyl)-1, 3, 5-triazine was obtained by the nitration of 2, 4-diamino-6-phenyl-1, 3, 5-triazine. 2-Amino-4-(p-nitroanilino)-6-phenyl-, -4-(2, 4-dinitroanilino)-6-phenyland -4-(2, 4-dinitroanilino)-6-(mrnitrophenyl)-1, 3, 5-triazines were obtained from 2-amino-4-anilino-6-phenyl-1, 3, 5-triazine.

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Soluble polyphenylsilsesquioxane was obtained almost quantitatively from the reactions of tripotassiumphenylsilanetriolate aqueous solution with (1)acetic anhydride and (2) chloroform, and from (3) hydrolysis of phenyltrichloresilane with aqueous amine solution according to the following schemes:
(1) PhSi(OK)3 + 312 (MeCO)20. 1/n (PhSiOi.s)n + 3 MeCOOK
(2) PhSi(OK)3+3/4 CHC13-1/n(PhSiOi.s)n+9/4 KC1+3/4 HCOOK
(3) PhSiC13 +3/2 H20+3/2 diamine.1/n(PhSiOi.s).+2/3 diamine-2 HCI
All the reactions were so undertaken as to proce6d through interfaces of binary liquid layers at refluxing temperature by use of MIBK layer as a medium. Intrinsic viscosity of the initial prepolymer ranging from 0.06 to O.13 increased gradually by heating the solution with O.1% KOH.
Analogous reactions which involve co-hydrolysis of phenyltrichlorosilane and equimolar amount of each diphenyldichlorosilane and of methylphenyldichlorosilane were found to give cotresponding soluble polysiloxanes with cyclotetrasiloxane segment in the structural repeating unit.
Co-hydrolysis of a mixture of phenyltrichlorosilane-vinyltrichlorosilane (1:1) also gave asoluble and infusible polymer.

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The reaction of C6H5CH2CH3 and C12 in the presence of ZnCl2-KCl-NaClfused salts (3:1:1 mole ratio) or CuCl-KCI-NaCl fused salts (3:1:1 mole ratio) under N2 carrier gas have been carried out at different temperatures (at 250, 350 and 4500C) and the salt effect on the distribution of the products was studied.
Non-catalytic gas phase chlorination of ethylbenzene afforded preferably ec-chloro and 3-chloro ethylbenzene while the chlorinatien through fused.salts gavestyrene type compounds along with af-chloro and B-chlbro ethylbenzene.
In the latter reaction with CuCl-salts, the yield of styrene type products was larger than that of the reaetion with ZnC12-salts, although ZnC12-salts was found, inour previous study, to be more catalytically active than CuCl-salts for the dehydrochlorination.
The dehydrochlorination of C6H5CHCICH3 in the presence of fused salts(ZnCI2, CuCl)gave predominantly styrene, while the dehyrochlorinationof C6Hs(CH2)2Cl was not observed under the same conditions. Therefore, the styrene derivatives obtained from the reactions through fused salts is believed to result predominantly from the dehydrochlorination of a-chloro ethylbenzene derivatives.
In the non-catalytic gas phase chlorinatien of ethylbenzene, the presenceof HCI which can form z or a complex with aromatic compounds diminished therelative reactivity for the chloro substitution of cu-position to B-positien of ethylgroup.
From the above results, the fact that the chlorination throughZnC12 salts gave less amounts of styrene derivatives than the chlorination through CuClsalts did may be explained by the decrease in the relative reactivity ofa-position of ethylbenzene for the substitution due to the formation of z or a complex of ethylbenzene with ZnC12.

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Reductionof -nitronaphthalene with su des was studied. The selectivity of the reduction to a-aminonaphthalene was decreased with increasing concentration of sulfides. lt was found desirable to use sulfides which aged for one day 3 times more than the ameunt theeretically required. The higher the reductien temperature, the higher was the selectivity to a-aminonaphthalene. The presence of FeCls improved the selectivity, while the increase in OHm concentration decreased the selectivity to a-aminonaphthalene# From these results, the optimum reduction condition to give 93% of a-aminonaphthalene was established.

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It was found that nitration of toluene with nitric acid in the presence of anhydrous aromatic sulfonic acids on the various supports, greatly increase the ratio of para isomer to ortho isomer and the yield of monenitrotoluene, compared with nitration without any supports.
Viscous liquid sulfonic acids, such as toluene-2, 4-disulfonic acid, m-benzenedisulfonic acid and mixture of e-, m- and P-nitrobenzene sulfonic acid etc., were especiaHy effective and the most suitable support was diatomaceous earth (Celite-545).
Thus, by use of toluene-2, 4-disulfonic acid, m-benzenedisulfonic acid, mixture of o-, mand p-nitrobenzene sulfonic acid, chlorobenzene-2, 4-disulfonic acid and sulfonated polystyrene on the Celite-M5, the P/o ratio and the yield of nitrotoluene were 1.61, 96%, 1.53, 92%, 1.50, 91%, 1.47, 90% and 1.42, 77% but in. the absence of Celite-545 those were 1.05, 72%o, 1.08, 81%, 1.25, 84%, O.91, 83fZa6 and O.70, 50%o, respectively.
The mechanism of the effect of aromatic sulfonic acids and the supports were also discussed.

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The reaction of safrole or isosaflole with aniline hydrochloride wasexamined, and the formation of methylenedioxybenzene or catechol was verified. Besides these compounds, the formation of p-toluidine, p-ethylaniline, p-propylaniline, e-propylaniline, 2-methyl-2, 3-dihydroindole, or 4, 4'-diamino-diphenylmethane has been confirmed. It was found that the isosafrole reacted easier than safrole.
The reaction of 3, 4-methylenedioxycinnamic acid and aniline hydrochloride afforded mainly catechol with a small amount of methylenedioxybenzene. The formation of p-ethylaniline, p-toluidine, 2, 4'-diamino-diphenylmethane, or 4, 4'-diamino-diphenylmethane was also confirmed.

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The reaction of linalool (1) with boron trifluoride er iodine has been reexamined, since the formations of B-pinene (3) were claimed in these reactions by several authors.
In the case of boron trifluoride, the dehydration of (Z) afforded B-myrcene and then Bmyrcene was isomerized partly to limonene. Thislimonene was further isomerized to aterpinene and isoterpinolene, and a formation of P-cymene occurred due to the disproportionation accompanying by a formationof p-menthane. Dehydromyrcene and many other CieHis F2 0r CieHi6Fg compounds were also formed simultaneously.
The more complex reactions occured in the case of iodine.
In every case, a formation of (3), a-pinene or camphene was never observed.
The results are shown in Table 1 and 2.

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Seven analogues of sclerin (1), which have different methyl substitution on the aropaatic ring were synthesized for the purpose of biological test. The compounds were mostly prepared by the application of the known methods used for the synthesis of (1), and also two new ones have been developed.
The physical and chemical data of the sclerin analogues, thus prepared, are summarized (Table 2 and 3) and compared. Especially, their behaviors support, though qualitatively the reasoning for the unusual stability of the anhydride ring in sclerin, previously made by authors and this phenomenon represents a good example for steric population control, currently proposed by Milstein and Cohen.

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Ethylen-vinyl acetate copolyrners (EVAc) containing 11.2 and 13.8 mol % of vinyl acetate unit were used throught this work. After purifying by a sequence of dissolutions in toluene and precipitations with methanol, the EVAc films having uniform thickness of 60 a to 160 a were prepared from toluene solutionsby evaporating the solvent on a glass plate at room temperature. The hydrolyzed films (EVAl) were obtained by suspending the EVAc films in a methanol solution of sodium methoxide at 0-400C Partially hydrolyzed films which consist of three layers (EVAl-EVAc-EVAl) were also prepared from the EVAc films by adjusting the reaction conditions of hydrolysis.
The transmission of helium, hydrogen, carbon dioxide, oxygen, argon and nitrogen was studied in the films of EVAc, EVAI and EVAl-EVAc-EVAl. By using a time-lag method, the permeability coefficients, thediffusion coefficients and solubility coefficients were measured at 10-.-60'C. The data of the EVAl films were compared with those obtained in the EVAc films. Both the permeability coefficients and the diffusion coefficients of the EVAL films at constant temperature were much lower than those of the EVAc films. For example, the permeation and diffusion results for carbon dioxide, oxygen, argon andnitrogen in the EVAl film derived from the EVAc film containing 13.8 mol % of vinyl acetate were about 1/50 of the values in the EVAc film. However, the apparent energies of activation for the permeation and diffusion in the EVAl film were almost eqaul to those of the EVAc film and polyethylene. No increase in crystallinity was observed upon hydrolysis, so the reduction of permeation and diffusion was ascribed to the effect of chemical composition changes, namely to the immovability of polymer chains due to the formation of hydrogen bonding. Barrie, et al. reported that PID', solubility coefficients (S') of gases in laminated films, which were obtained from the apparent permeability coefficients (P) and the apparent diffusion coefficients (D') were different from the solubility coefficients(S) which were obtained from an equation of the equilibrium solution17. However, the solubility coefficients (S') of helium and nitrogen in the three layered film, EVAl-EVAc-EVAl, were found to be almost equal to the solubility coefficients(S). This was assumed to be due to the similarity of the solubility coefficientsof these gases and the large difference of their permeability coefficients in the EVAc film and the EVAl film.

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The mechanism of the reaction of aliphatic amide (Q-CONH2: Q=H, C2H5, n-C3H7 orCH2=CH) with formaldelhyde in the presence of sodium hydroxide was studied kinetically in water at 300G. The rate was found to be expressed by the following equation:
R0= -d[F]/dt=k[Q-CONH2] ENsOHI [F]1-O where [F]1-0 means that when the concentration of formaldehyde vias less than a definite value ([F]0), the reaction was of the first-order with respect to formaldehyde, however, in a higher coticentration of formaldehyde than [F]0, the reaction order of formaldehyde became zero. The more the Q-group had electron attracting character, the more the rate increased. It was concluded that Q-CONH ion formed by the reaction of amide with 0H existed in the center of a solvated cage and reacted only with formaldehyde included with in the cage, but would not react with formaldehyde inthe outside of the cage.

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Styrene (St) was pelymerized when the divalent chromous acetate, (Cr2+)-CHCIs system was used as initiator. In the case of [Cr2+]/[CHC13] 20, the rate of polymerizatien decreased with increasing [Cr2+].
The termination reaction with Cr2+ was studied in detail using a, a'-azobisisobutylonitrile (AIBN) as initiator in the presence of Cta2+. The rate of polymerization decreased with increasing Cr2+ and the rate constant of termination reaction of polystyryl radicalwith Cr2+ was found to be 74.61/molosec. Whereas, the polymerizations of methyl methacrylate and acrylonitrile were inhibited by Cr2+. This difference of termination effects was discussed in terms of the e value of the monomers.
Due tothe combination of Cr2+ with p-benzequinone(P-BQ), it was found that the termination effects of Cr2+ and p-BQ disappeared, because P-BQ reacted with Cr2+ to produce an inert oxidation product.

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The effect of ethers [propylene oxide (P0), tetrahydrofuran (THF), epichiorohydrin (ECH), 3, 3-bis(chloromethyl)oxacyclobutane (BCMO), and j3-chlorophenetol (-CPT)] on the polymerization of methyl methacrylate (MMA) was investigated.
The polymerization rate in P0 and THF was the same as that in benzene.In the case of polymerization of MMA in the presence of ECH, BCM0 and j9-CPT, itwas found that the polymerization rate and the degree of polymerization increasedwith increasing amount of these ethers. These accelerating effects was clarifieddue to a decrease of the termination rate constant (Kr) with an increase in viscosity of the polymerization systems. The chain transfer constants (C8) of these ethers were determined from the degree of polymerization with a correction forviscosity term.

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It was found that triiodide ions (I3-) were prgduced from the mixture of polyamine polymer (1) and iodine molecule (12) via charge-transfer (CT) complex formation between them, Its velocity was extremely greater in(1)-I2 system than in its low molgcular weight model compounds-I2 systems. The causes of accelerating the reaction in polymeric systems have been clarified. They were the increments of local donor concentration and of local polarity around the active sites in the polymer chain because the donor nitrogen atoms are fixed on the main chain in contrast with those of the monomer analogues.
Then the reaction of (1) with 7, 7, 8, 8- tetracyanoquinodimethane (CQ), which is one of the rr-acceptorsof large size, was investigated. The rate of formation of CQ anion radicals in polymerie system (pseudo first order reaction) was almost the same as that in itsmodel compound systems. This might be explained by the steric hindrance-of the polymer chain because CQ molecule was too large to approach to the donor sites ofthe polymer chain as I2 in the (1)-I2 system. It was also suggested that this reaction proceeded through direct one electron transfer from donor to acceptor moieties and not through CT complex formation.

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The reduction (electron-transfer reaction), of'cis-[Co(III)(en), PVPCI] C12 PVP:poly-(4-vinylpyridine) by Fe(ll)Z or FeEDTA2- (ethylenediaminetetracetato-iron(ll)2-) was studied.The reductien by Fe(ll)2 was very slQw and the reactivity of PVP complex decreased to 1/3.v 1/5 and was lower than that of corresponding monomeric Py.(pyridine) complex, beeause of the electrostatic repulsion. On the other hand, the reduction by.FeEDTA2- was very rapid because of the electrostatic attraction ahd the reactivity of the' PVP complex' was higher by the factor of 20 than the Py complex. An increase in the degree of coordination of PVP to Co(M) brought abo'ut an increase in the rate constant ratio (kpvp/kp, , kvrate const; of PVP complex, kp, rate const.of Py complex) and an ihcrease in the ionic strength decreased the ratio. This result was interpreted in terms of the electrostatic interaction of FeEDTA2 with the PVP complex as a polycation, These electrostatic-effect were, discussed, by comparing it with the catalytic action of, polyelectrolyte, in the ioni, c, reaction

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It has been found that the polymer aggregates (emulsion particles) were formed in the region of the particular degree of neutralization when ethylenediamine was added to aqueous polyacrylic acid solution. Then its mechanism was studied by the use of turbidity, viscosity and conductivity measurements. The results obtained were as follows. 1) The viscosity of polyacrylic acid-ethylenediamine was much lower than that of poly(acrylic acid)-n-butylamine and curves of the viscosity vs. degree of neutralization showed the maximum and mium values.2) lt was proved by measuring the conductivity of system that ethylenediamine was adsorbed by polyacrylic acid. 3) ln a copolymer bf acrylic acid and ethylacrylate, the turbid region decreased with increasing mole ratio of ethylacrylate, and emulsion particles were not formed more than 10 mol%. 4) With amines other than ethylenediamine, polyL-valent amines such as diethylenetriamine and triethy1enetetramine which had the ethylene segments only formed the emulsion particles inaqueous polyacrylic acid solution.
From these results, it was concluded that emulsion particles were formed due to the hydrophobic property of polyacrylicacid caused by the following mechanism: Ethylenediamine molecules were combined with the neighboring earboxyl groups by an ionic reaetion and then the ethylene segment of ethylenediamine molecules arranged appropriately along the main chainofpoly(acrylie acid).

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A new photosensitive polymer with pendant cinnamic ester group was prepared from poly(vinylalcohol) bY graft ring opening alternating copolymerization with glycidyi cinnamate and phthalic anhydride in hexamethyl phosphoramide.
The relative photo sensitivity of the obtained graft polymer containing 5-nitroacenaphthene as a sensitizer was ca. 22.4 times higher than that of KPR, and ca. 4 times higher than that of poly(vinyl cinnamate), which has the same degree of polymerization as the graft of polymer.

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A new simple notation describing close-packed structures was given. The layer sequence of close-packed anions was represented by the symbols of polytypism, and the arrangement of cations in the tetrahedral and octahedral voids was indicated briefly by the fractions of the voids occupied. A rhenium trioxide and a cristobalite.q, tructures were expressed in terms ofdefect of anions fromclose-packing.The arrangement of cesium chloride was also represented by a stackingof ionic layers.The structures of about a hundred inorganic compounds were described (Table 2N7), and the correlation of these structures was discussed.

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The detection of a short circuit of electrodes in the mercury cell was successfully carried out by passing by-pass current to the Pt anode probe. The amalgam ripple on the cathode was found to be unexpectedly high (the thickness of the amalgam ripple:0 5-1.Omm), for which fact the technological analysis would be expecte

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The reaction of butylmagnesium bromide and allyl chloride in the presence of nearly equal amount of the nickel or cobalt complexes coordinated with phosphine yielded large proportions of octane (56-v61%) and 1, 5-hexadiene (40N59%), which is in marked centrast to those propylene 70%e and butenes 71% obtainedin the presence of catqlytic amount of the metal chlorides.
The addition of hexamethylphosphortriamide (2 equives to BuMgBr) to the latter reaction conditiengave the similar effect as in the case of the coordinated metal complexes.
The principal effect of the ligand was deduced to lie in the stabilization of thedibutyl metal interrmediate from'butylmagnesium bromide rather than rr-allylmetal intermediate.
TheLdependence of the products on the quantity of a, a'-dipyridyl nickel and cobalt chlorides showed that the ligand effect becomes appreciable only at a higher concentration ( 10-S) of the metal complexes.

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The products obtained by the nitration of ethyl benzen, isopropyl benzene and halobenzenes with nitric acid and 2, 4-teluenedisulfonic acid (TDS), supported on diatomaceous earth (Celite-545), showed considerably higher para-ortho ratio (P/o) than that observed in the nitration with nitric acid and sulfuric acid (mixed acid nitration), similarly as the case ef nitration of toluene.
The results are shown in Table 2.
The nitration of e-xylene in a similar manner gave also high 4-nitro-o-xylene/3-nitro-e-xylene ratio and mononitration yield (3.02 and 90%) than those observed in the nitration with nitrie acid and sulfuric acid (O, 99 and 80%).

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Sulfur monochloride and carboxylic acids do not reqct without catalyst, but react, easily in the presence of catalyst such as reduced iron powder, ferrous chloride, sulfate, oxqlate and formate, and ferric chlQride, sulphate and acetate giving acid chlorides. Arematic mpno- and dicarboxylic acids (isophthalic and terephtha1ic acids, with exception of phthalic acid)'and lower fatty acids produced acid chlorides in geod yields. Adipic aid, aliphatic dicarbexylic acid, produced small quantity of acid chloride in the presence of ferric acetate enly, . but in the presence of ferric acetate and pyridine the yield of acid chloride rose to about 5Q%.

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Electroinitiated polymerization of N- Vinylcarbazole was studied in various solvents It was found that the polymerization proceeded in acetic anhydride and acetonitrile solutions containing lithium perchlorate.
UV-and IR-spectroscopic studies showed that the structures of the polymers so formed were similar to those of the polymers produced by the usual cationic polymerization. Furthermore, the presence of very active species in the electrolyzed solution suggests that acyl grgups or hydrogen cations which were produced by electro1ysis of acetic anhydride or acet6nitrile, initiated the polymerization.
Moreover, it was assumed that the polymerization initiated by electrolysis proceeds via a cationic mechanism.

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