It was found that extra absorption bands appeared at 288 and 464 nm when iodine was dissolved into aqueous dodecylpridinium chloride (DPCI) solutions below CMC, When the conr centration of DPCI exceeded its CMC, a new absorption band appeared at 366 nm accompanying the disappearance of 288 and 366 nm bands. These two bands are due to the charge transfer interactions of iodine with DPCI molecule and DPCI Micelle, respectively. By use of thess charge transfer-bands, interactions between DPCI and heptaethylenegrycol dodecyl ether Ci2E7 were studied for the following four cases.
Case 1;
Case tt;
Case;
The cO ncentration of both DPCI and Ci2E7 were below CMC. The Ci2E7 concentration was above CMC, while the DPCI concentration was below CMC ha de The DPCI concentration was above CMC, whereas the Ci2E7 concentration was below CMC.
Case N; The concentration ef both surfactants were above CMC.
In Case 1, no interaction could be detected between the two surfactants.
In. Caces, and V, characteristic changes in abs rpti n spectra, which could be explain ed on the assumption of formation of mix ed micelles between DPCI and CmE7, was observed.

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Various porous glasses were prepared by the extraction with HCI of borosilicate glasses (NazO 5 B20s, 12.7rSiO2), tchich was vafiotisly phase-separated by c6ntrolling the temperature and period of heat treatment. lsotherms of benzene sorption at OeC on the porous glass changed regularly in shape depending on the conditions of the pretreatment (Figs.1, 2, 3 and 4). Table 1 lists extracted fraction f (g!g) Qf each specimen, together with sorption characteristics obtained from BET plots and the isotherins. Analogous data from me. tnth. anol isotherms are given in Table 2. These results were discussed on the basis of capillary condensation theory. The shape of the benzene isotherm are different from that of methanol in some cases (Figs.5, 6), but pore distribution curves calculated from them agreed with each other except small difference in the very low pressure region. Figs.7 and 8 show that the theoretical condensation isotherms for the assembly of fine spheres arranged in the closest packing are in fair agreement with the experim. ental isotherms, when the granules of Jsepar-ate-d. pba-se a-r. e grgwn"up syfficignt, Ly. (ca: 5. ---t600 A in diameter). Volume of pore space ge calculated by f/2.20(1-f) is given in Fig.9by solid line and also in the last cQlumn of Table 1. Experimental values s asL, btained from the saturated amount of sorption as, are in agreement with thsO witl in 10%e of error for pecimens in which granules have grewn up sufficiently. Large deviations in Fig.9 are found with the specimens giving the type (1) isotherm and might be attributed to very fine pores possessing molecular-sieve effect for methanol as well as for benzene molecules. Thus, on the basis of capillary eoRdensation theory, it is concluded that regular change in isotherms is due te the growth of granules originated from silica-rich phase, and the pore space effective for sorption is formed by dissolution of the intergranular

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Solubilities of copper(1) chloride in hydreehloric acid solutions (O.05, v3. O mol/1) centaining perchleric acid were measured at 15-v35"C and under constant ionic strengths of O.2-v6.5 mol/1.
The data were interpteted satisfactorily by assuming the presence of three complexes, CuC12-", CuCls2'-, and CuCls3-, in the solutions. The equilibrium constants of these three eomplexes were determined and cdrrelated as functions of ionic strength and temperature of the solution. The solubility data obtained by the present authors and previous investigators were compared with those calculated using the empirical equations obtained in the present work. As seen in Fig.7, the Qbserved solubility data were in good agreement with the calculated values within 10%.

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Tbe difference of the catalytic activities between NaX and NaY under the influence of the'k calcjnqtign temperqture, the addition of water or pyridine, and the degree of decationati6h 16i methylmigration of anisole was studied using the flow reactor.
T. he orqer of gatalyt. ic. activities at t-he tgmperature range from 275 to 400eC was NaX NaY, contrary to usual atalytic activities of zeolites: Y type Xtype.
A. pisgle copy-er-s. ion"op NaX decreased with increasing calcination temperature above 450°C as REX above 400°C, while NaY has no influence on the calcination temperature.
addition of pyridine for dehydration of isopropanol, its conversion on NaY decreased a little.
The catalytic activities of NaX and NaY were increased as they were decationated gradually, and the addition of water of NaX, decationated, allowed anisole conversion to increase constantly to 10 mol%e regardless of the degree of decationation.
The reaction of anisole over NaX, NaY and NaX, added water or pyridine, was explained by zero order kinetics and thb value of activation energy was as follows; NaX: 16.6, NaY: 25.8, NaX added water: 16.8N17.6, NaX added pyridine: 22. O kcal/mol.

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The isomerization of cis-2-butene was investigated over zinc sulfide catalyst. The effects of the pretreatment and the impurity were studied in order to reveal the correlation between the surface properties and the catalytic behavior.
When the pure-ZnS was evacuated at elevated temperature. s up to 500 OC, the surface -area sh wedarked decreases d e t, sintering, D, ping with A13 r Ga3+, h, weve seemed to, retard the sintering.
The concentration of the acid sites on the surface of the pufe-ZnS was in the comparable order with those of the typieal solid acids, such as silica-alumina and zeolites The number of the relatively stronger acid sites(rg 1.5)was increased by the pretreatment of evacuation, while the catalytic activity contrary lowered. ln the case of the Ga-doped ZnS, the surface acidity erresponding to the weaker acid (1.5sHe S 6.8) was notably increased and the catalytic activity was also fairly promoted.
On the basis of these results, it should be concluded that the catalytic behavior of the catalyst can not be explained simply by the acidic properties of the surface.

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The spectral sensitization of photoconductive poly(N-vinylcarbazole)(PVK) was studied by using cyanine and styryl dyes. The dyes used were symmetrical carbocyanine ones. a. nd styry1dyes had benzothiazole br 3-dimetylindQle ring in their structures. Two structu. ral facto-rsun. gg as PVK the dyes were investigated because they showed excellent properties for these dyes sensitizer. One of the factors was an 2V-alkyl effect of the heterocyclic ring of these dyes. As a result we found that a long-chain N-alkyl like n-octyl showed high solubility in PVK and also remarkable high sensitivity. For instance, the PVK m including O, 048 m 1 of 3, 3i di-n-octyl-6, 6'dinitrobenzbthiac4rbocya-nin-e h. ad. an gec. t. ro. phgtograp. h. ic sens, itivit. y of, Eii2=, '22fux i sec. r ln comparison with this, 3, 3Ldiethyl-6, 6' dinitrobenzothiaearbOeyanine showed relatively low sensitivity of Ei/z=436 lux"sec. As the other factor, an effect oC s"bistitutfgn The was investigated, by using 6-position of benzothiazole and 5-position of 3-dimethylipdo'le. substituentsT had the groups of different elecSron affinity such as OCHg, CH3, H, 1, Cl?, Br, NOa, etc. The"sensiti'zingT effi6iency of dyes of benzothiazole increased with increasing electron affinity bf substituentsl On the other hand, the 3-dimethylindole showed less changeable t. epden. cy. Acc6rding to the eXperimental results, when 6, 6' pe. sitions of 3, 3' di-n-octylbenz-othi4garbgcyanine were s ituted with NO gt ups, the sensitivity increased 5, 8 times, but when 5, 5' of twQ stractural factors wexe Qbserve. d Qn styryl dyes,

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Poly(glicidyl cinnamate)(PGC), a new photosensitive polymer was prepared by the condensqtion reactibrf of epichlorohydrin rubber with potassium cinnamate in aprotic polar solvents such as hexamethylp. hosphoramide(HMPA), dimethylsulfoxide(DMSO) and dimethylformamide(DMF).
The effects of temperatures, solvents and catalyst on the reaction were investigated. lt was observed that the condensation reaction proceeded more readily in HMPA than in DMSO and DMF, and the degree of esterification of PGC obtained in HMPA was higher than that in the others. The degradation of polymer was found to occur as a side reaction during the condensation reaction.
PGC was also prepared by the Schotten-Baumann reaction from cinnamoyl chloride and polyglycidol which was obtained by the cationic polymerization of glycidol.
Some properties of PGC prepared from epichlerohydrin rubber (PECH) with potassium cinnamate were measured. The relative sensitivity of PGC containing 5-nitroacenaphthene as a sensitizer was ca, 8 times higher than that of KPR; observation for the hange of infrared absorption of C C at 1640 cmin i in PGC caused by ultraviolet irradiation suggested that PGC crosslinks more rapidly than polyvinylcinnamate. The glass transition temperature of PGC was found to be 3

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Effects of 6eCo-r irradiation on the'electrode reactions of an, alupainum metal in water were investigated. lrradiation (up to 2.4 ZO6 R hr) caused a shift of the Al-electrode potential by several hundred millivolts to a more negative value. The irradiation also increased the anodic polarization urrent and decreased the cathodic polarization current. The results can be explained qualitatively in terms of radiation-produced electron-hole pairs in a barrier layer of an aluminum surface.

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States of the interfacial Iayer at the desalting side of an ion exchange membrane under water decomposition conditlons in. sodium chloride solution were observed by the Schlieren-DiagonaI method which was previously reported by the author. Results obtained are as follows;
(1)The Iimiting current densities estimated from current-voltage curves agreed with those at which the concentration at the membrane surface reached (Fig.1, 2a: nd 3).
(2) Relation between the Iimith g current density and the thickness f the interfacial layer was interpreted consistently by taking the concentration distributi n in the layer i: nto acc unt for the balance of so1 te in the layer(equati n(3))
(3)In the process of the interfacial Iayer formati n, the concentration decrease at the surface of the cation exchanger was more rapid than that ofl the anicn exchanger. Temporary water decompositlon phe: nomena for a short period were occasio: nally observed, as a result, at the early step of the course even when the current density apPlied was Iower than the limiting one(Fig.6and 7).
(4)Vibrational concentration changes were observed in the thin 1ayer at the cation excha nger under water decomPosition conditions. It seemed to be ide ntical in mechanism to the pulse current"phenomena reported by T. Yamabe and M. Sen6. At the anion exchanger, however, the concentration distribution remained stable even under water dec6mposition c nditi ons(Fig.8).
(5)Under water decomposition conditions, the concentration distribution in the interfacia11ayer of cation exchanger showed complicated con guration consistingof about 4 parts(Fig 9).

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By irradiation with a low pressure mercury lamp, photolys is of oxalato-titanium(N) complex was studied in aqueous solution at constant pH with excess amount of oxalic acid to prevent any secondary reactions, such as hydrolysis of the primary product.
In the presence of excess amount of oxalic acid, the composition of oxalato-titanium(N) and ()complexes were investigated spectrophotometrically and were assumed t be TiO(C20i)2 2 and Ti(C20k)2
Irradiation of a solution of oxalato-titanium(N) complex in excess amount of oxalic acid, in which the molar ratio of Ti(N) and oxalic acid is 1: 10, led to photoreduction and hydrolysis of the complex. The photoreduction reaction forms an oxalato-titanium()complex with evolution of carbon dioxide. The hydrolysis reaction gives a precipitate of titanium(N) hydroxide with evolution of carbon dioxide and carbon monoxide.
Furthermore, a photosensitized reaction of oxalic acid by the oxalato-titanium()complex oceured during the irradiation. Consequently, oxalic acid decomposed to carbon dioxide and earbon monoxide.
The initial reduction rate and the final reduction ratio decreased linearly with increase of pH value of the sample solution. Thus, it was found that H" ion contributed to the photoreduction of oxalato-titanium(N) complex.

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The synthesis of europium sulfide by the reaction of europium oxide with carbon disulfide was investigated, and oR these products the decomposition processeses on heating under some atmesphere were studied.
The oxygen content was determined by fast neutron activation method, and the valence stqte of europium ion was estimated by the measurement of paramagnetic susceptibility at room temperature.
By heating europium oxide in carbon disulfide vapor, Eu3S4 containing small excess sulfur was formed at 500. v600 C and EuS was formed at 900NIOOOeC. But, the contamination of small amount of carbon was observed in this case. The oxygen contepts in these Eu3S4 and EuS were O.9Nl.1 and O.2. vO.3, respectively.
Europium monosulfide was also obtained by thermal decomposition or reduction of Eu3S4 in the stream of nitrogen or hydrogen. The oxygen content in the resultant europium monosulfide was also O.2, wO.3.
Europium sulfide was very sensitive to oxidation. Therefore, under the atmosphere of oxygen europium monosulfide was oxidized to Eu202S and Eu, S4 at temperature above 200UC. By further oxidation, small amount of sulfur was removed at 650, v670 C, and the mixture of Eu202SO4and Eu2(SOs)s was formed at 750N8000C.

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Stable complex compounds ef dimethyl sulfoxide(DMSO) with lanthanoid perchlorates of the formura M(CIO)3, nDMSO (M=La, Ce, Pr, Nd, Sm, Eu, Gd and Tb, n ns 8; M=Dy, Ho, Er, Tm, Yb and Lu, n s 7) have been prepared, and their infra-red spectra in the 4000-v200 cmm-i region were measured. The spectral evidences suggested that coordination of DMSO occurred with its oxygen atom for all lanthanoid metals. The frequencies and intensities of v(M-O)were found to depend on the ionic radii of the lanthanoid. On the basis of the results obtained it was concluded that the strength of M-O bond increased with decreasing ionic radii, and these co plexes contained both seven-and eight ordination compounds.

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The substitution reactio: ns between ind um()a: nd zinc()-trans-1, 2-cyclohexanediaminetetraacetate complexes(Zn()CyDTA)and between indium()and zine()-ethylenediaminetetra acetate c. mplexes(Zn()EDTA)I cetate er s, 1uei ns were investigated by measuring the change in p 1ar graphic diffusi, n current, f indium()with time, The rate equati, n f, r the reaction was of rst-order with respect to the concentrati n of indium()and that of the complex. In the s, ubstitution reaction between indium()and Zn()EDTA complex, there was a direct indium()I n attack, n the c, lex, while n, direct indium()i, n attack, n the Zn()CyDTA complek7 The rate constants determined at ionic strength of o.2 "at 2s. o. eC indicated. th. at the reacti ns thr ugh hydr, x, indium()i, ns and m, n, acetat, indium()c, mplexes pr ceeded m, re ions. This was considered rapidly than th, se thr, ugh the c, rresp, nding hydrated indium()to'be"mainly due to the Mdifference in the rates of exchange of coordinated water molecules in indium()ions a iff 5i6ffcMOe in the rate of reSaction and the reaction paths may be explained in terms of a difference in size and stereo-constitution in coordination of EDTA and CyDTA.

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Ag was determined by two methods. The principle pf method A was tha. t the liberated Cu2+rm was titrated with EDTA after the exchange reaction between Cu2 in (DDC), Cu and Ag+. And the method B had a base that the excess Cu2 was titrated with EDTA after filtering (DDC)Ag and (DDC)2Cu precipitates which was formed by the additiori of known'amount of (DDC)Na and known amount of excess Cu2 tg sample solutign.
Method A: Sample solution, 10 ml of chloroform, and 10 ml of disodium hydrogenphosphatecitric acid buffer solutio: n(pH 5.0)were taken into the separatory funne1 100 m containing lo ml of O. Ol mol/1 (DDC)2Cu chloroform solution The total volume of aqueous phase was adjusted to 30 ml with water. Being shaken for abgut 15 minu-tes, i. t was st-oo-d for abogt io mi: nutes. A: n aliquot(15 20m of the aqueous phase was taken into a Erlenmeyer fl ask, After the addition of 10 ml of methanol, the solution was diluted to about 30 ml with watEr, and was titrated with O, OOI mol 1 EDTA, PAN being used as indicator.
Method B: Sample solution was diluted to about 25 ml with water, and 5 ml of 10 methanel aqueous solution of 4*10m2 mol 1 (DDC)Na was added, After' st-an-d. ing for abo-ut-10. minutgs, (bDc)Ag precipitate was filtered off and was-hed, . aLnd-5ml of C-u.2'hsolutio. n. of 2Ax lO"2-mol/l bvas add6d to the filtrate. Being stood for about 10 minutes (DDC)2Cu precipitate formed was filtered off and washed with acetic acid-sodium acetate buffer solution pH 4, 0). Twenty ml of methanol was added to the filtrate and Cu2 was titrated with O. Ol mol 1 EDTA using PAN as an indicator.
By means of the, proposed method A, O.05. v6 mg Ag could be determined, and by the method B, 6-v14 mg of Ag was dete. rmined satisfactorily.

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Iodine dose not react with sodium azide, but it is known that the following reaction is catalytically prornoted by the presence of micro amounts of sulfur compounds.
2NaNs 12 - 2 Nal 3N2
The catalytic effect of sulfur compounds en the reduction of iodine is applied to the photometric determination of ultramicro amounts of thiosulfate.
One milliliter of an aqueous solution (1*10-3 N in KIO, and 1 N in KI) is placed in a glass tube with a glass stopper. Then 1 ml of the 1. O N acetic acid and 3. O ml of the sodium azide selution (20 g/100 ml) are added. To the solution being kept at 250C, 5. O ml of the sample solution of the same temperature are added and mixed. At 3 min after the mixing, the absorbance of the solution is measured at 350 nm.
The available range of the present method covers from O. Ol ppm to O.15 ppm of thiosulfate in 5 ml of the sample solution.
The standard deviation is O. OOI and the variation coefficient is O.91%o at the S20s2- level of O.1PPm. Fe(), Cu(), SO32, and CN-interfere with the determination of thiosulfate,

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Two kinds of crosslinked copolymer were prepared by respective suspension copolymerization of vinyl acetate with vinyl chloride and vinyl acetate with vinylidene chloride, and by subsequent crosslinking with sulphu. Crosslin: ked copoly(vinyl alcoho vin. yl chloride)an. d copoly (vinyl alcohol-vinylidene chloride) gels were obtained by hydrolysis of the abeve copolymer with aqueous methanolic sodium hydroxide solution. When poly(ethylene glycol) or poly(vinyl acetate) was passed through a column packed with the gels, it became evident that larger species were completely excluded from the gel phase, whereas smaller species penetrated the gel particles. Consequently, after the passage through a bed of the gels, the solute molecules were fractionated into two groups. This behavier is remarkably different from that of ordinary gels. To explain this phenomenon, it was assumed that the surface of the gels was made of thinly crosslinked layer and that the inner part of the gels was made of loosely crosslinked structure or no crosslinked one.

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When the ge-paratigns. of the fission prod-u. ct ar-e carri'ed out by means of cation exchange resin chr-om" qtographic method, cations contained in F, P, are adsorbed on the resin, while anioW as MoOA2, . TcOk, 103ew, 1 and RuO42ww were passed through the resin column. ln order t6wasD c. arried-out by spraying the detection reagent solutio- Autoradiographic method was' used for radieactive anions.

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The synergistic effect of 1-butanol(BuOH) on the solvent extraction of vanadium(V) with 2thenoyltrifluoroacetone(TTA Htta) was investigated and the extraction reaction was explained in terms of the esterification: VO2' 2Htta. BuOH, =VO(tta)2(BuO), H20 H, The extraction constant of the above reaction was obtained to be K..=1.7 10S. ln contrast, in the case in which tri-n-octylphosphine oxide(TOPO) was used as an additive, the synergistic effect is attributable to the reaction: VO2' Httaor, TOPO, VO2(tta)(TOPO)er, H",
The synergistic extraction of vanadium(N)was found to be explained by the formation of an adduct: VO2 2 Htta.. g=VO(tta)2, 2 H" and VO(tta)2, g Sg=VO(tta)2S, g, where S denotes an additive. The stability of the resulting adducts decreases in the order: TOPO isoquinoline quinoline 1-butanol.

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The rates of quaternization of substituted pyridines with dodecyl bromide were measured in methanol and dimethylformamide(DMF). The effects of Substituents and solvents on the reactivity of pyridines were discussed. The rates of the reaction showed larger values in DMF than in methanol and increased with the electron repelling power of Substituents. The isokinetic relationship was seen between E and ASa except for 4-aminopyridine. The excellent linear relationships, given by the following equations, were observed between log k and PKa "of pyridines except 4-aminopyridine, but the deviations from the Hammett line were also noticed for pyridines substituted with amino, benzoyl, alkexycarbonyl and cyano groups at 4-position. These deviations were considered to be attributed to the localzation of rr-electron on pyridine ring induced by the nuclear nitrogen atom and the 'variation of solvation on the substituents.
log k=0.157 PKa-5.250 (in DMF at 50°C)
log k=0.136 PKa-4.586 (in methanol at 750°C)

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Six hexadienes, straight-chain and cyclic, were allowed to react with equimolar amount of mercuric acetate in acetic acid at 130Av140eC, and the relationship between acetoxylated products and the structure of the starting dienes was investigated. Mixtures of mono and di-acetates were formed from 1, 5, 14 and 1, 3-hexadienes, and the ratio pf monoacetates to diacetates increased depending on the ratio of the amount of dienes to mercuric acetate. However, only diacetates were obtained from other conjugated dienes. On the other haRd, from 1, 4-cyclohexadiene benzene sivas only obtained. General features of the acetoxylated products were as follows: 1 Monoacetates from 1, 5=1, 4 and 1, 3-hexadienes, and diacetates from the unconjugated dienes were proved to contain two double bonds.2 Diacetates from conjugated dienes were found to be monoeneiol diacetates, having a structural unit,
--6(oAc)-cH=cH---6(oAc)- or -6(oAc)-6(oAc)-cH=cH-.
The formation of these products can be interpreted by the Sequence involving formation ef an allylic mercury intermediate, subsequent ti-frozen type reaction and isomerization of the resulting allylic acetate.

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It was reported in the previous paper that BF3 e H20 had strong activity for the formation of benzoic acid (1) from dypnone (3) (A-cLeavage reaction).
In this paper the effect of heating on the activity of BF3. H20 was examined. On heating BF3. H20 liberated BFg to form mere stable BF3.2H20 which had only slight activity for Acleavage reaction,
In order to prevent the liberation of BF3 which brings about decrease in activity, BF3 gas was introduced to (3) or acetophenone (2) in the presence of BF3. H20. Liberation of BF, from BF3, H20 was practically prevented by introducing BF3 gas re than two times as much moles as BFseH20. From the studies on the effect of the aMount of BFS. HxO on the reaction of (3) or (2) under these conditions, it was feund that the increase in yield of (Z) was remarkable when BF3. H20 was introduced less than a mole to (3) or a half mole to (2).

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Diphenyl 6-nitrophthalide-3-phosphonate 1 was prepared in good yield by the condensation of 5-nitrophthalaldehydic acid with diphenyl phosphite.
In N-dimethylformamide 1 reacted with aromatic aldehydes in the presence of sodium hydride to give the cerresponding derivatives of 3-benzyli4en 6-nitrophthalide in high yield at room temperature.
When aromatic nitr so compounds were used in place of aldehydes in the above reaction, N. phenyl-4-n. itrophthalimides were obtained Phenylimino compounds formed interr ediately are considered to be transformed to the imides.
Diphe nyl 3-methyl-6-nitrophthalide-3-phosphonate was easily obtained by the methylation of 1 with methyl iodide.

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Lock obtained an isomerof 2, 3, 4, 5, 6-pentachlorobe: nzaldehyde oxime l a by oximation of 2, 3, 4, 5, 6-pentachlorobenzaldehyde 2 with hydroxylamine, but its con guration has not been clari ed. We obtained another iso: mer l b by oximationof 2 with hydroxylamine sulfonate 3. When the velocities of the de-acetic acid reaction to obtain nitrile 6 in pyridine of the acetate 5 a was compared with that of 5 b, we observed that 5 b completely changed, into 6 at 24 C f r an hr, but 5 a at 1150C for an hr. On heating, 5 a and 5b changed. to 6 and obviously the velocity of 5 b to change into 6 higher than that of 5 a Their NMR spectra showed general patterns of geometrical isomers of oximes, (DMSO-d6) 1 a 8.1(s, 1H, -CH=), 12.0(s, 1H, -OH); 1 b 7.6(s, 1H, -CH=) 11.8(s, 1H, -OH). Accordingly la and 1 b have Syn-and anti-con g, uratio: n, respectively. l b isomerized completely to 1a by heating it at the melting Point and then, by keeping it, and during the oxi ation reactions at higher temperatures. l a isomerized to l b by ultra-violet light. In Table 1, 1a / 1 b ratios under various reaction conditio: ns are shown.

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The reaction of thiophenol with diketene in the presence of small amounts of concentrated sulfuric acid offers a convenient method for the synthesis of acetacetylthiophenylester. An equimolar quantity of 100%--sulfuric acid was the. rp-ost u-eff- ective. cat. alys. t for the. r. e. actl on i, n, The synthesis of acetacetylthiophenyl- etrm at temperatures in the range from Oe to about 300ester was urfsuccessful by using 70%e-sulfuric acid, 70%-perchloric acid, concentrated hydrochloric acid, p-toluenesulfonic acid or triethylamine as a catalyst, or eyen arger amo. un. ts of c. on. ceptrated sulfUfic acid. Apph cation of this reaction to substituted thiophenols and thienapht. hols gave th6 corresponding-Acetacetylthioarylesters. On the basis of these obseryations, a mechanislin. of th e reactihon wds discussed.4-Methyl-2 H-1-benzothiopyran-2-ons have been prepared by 6Y610dehydration of acetacetylthioarylesters by the treatment. with. polyphos orig acid. The A oresceVnce of 4-methyl-2 H-benzethiopyran-2-ons was weaker in ethanol and stronger in perchloric acid than those of 4-methylcoumarins and 4-methylcarbostyrils.

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3-Methylene-2, 6-heptandione (2) was obtained by the dimerization reaction of methyl vinyl ketone (1), using the catalyst, consisted of cobalt or nickel dichloride.. and triphenylphosphine in protic solvents, at room temperature and under atmosphere. The yield of 2 became constant when the molar ratio of triphenylphosphine to metal salt was above 3: 1. ln case of Rh, Ru or Pd salt and triphenylphosphine catalyst, (2) and B-ethoxymethyl ethyl ketone (3) were obtained.

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New pigments were obtained by the condensation of 9, 9-dichlorofluorene with aromatic or heterocyclic diamines.
9, 9-Dichloroflorene was prepared by oxidation of fluorene with sodiqm bich ma e followed by chlorination of the oxidation product with phosphorous pentachloride. A mixture of 9, 9dichlorefluorene and each diamine in the mole ratio 2: 1.1 was heated with stirring in chlorobenzene or o-dichlorobenzene either in the presence or wifhout zinc chloride to give the corresponding pigment. The synthesized pigments are considered to have the symmetrical structures in which two mol of fuorene are combined with one mol. of the diamine through azomethine bonds, and show certain characteristic properties depending on the diamines employed. Their color is greenish yellow to brownish yellow except for the pigment derived from m-xyly ene diamine. The substituent effects on their color are found in the pigments derived from benzidines, while the conjugation effects are observed in the pigments derived from diaminoanthraquinones. Their solubility depends on their chemical structures; the pigments derived from P-phenylene diamine, 1, 4-diaminoanthraquinone and benzidines are slightly solub1e in several organic solvents, while those derived from heterocycl ic diamines-C 1, 5- and 2, 6-diaminoanthraquinoneS are praetieally insoluble in most organic solvents.
It is noted that the diamihes play a small part on the light. fastness of, the synthesized pigments, because most of the pigments have good fastness except for. the pigpaent derived from 4, 6-diamino-5-nitropyri midine.

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The effects of catalysts on the reaction of terephthalic acid and ethylene oxide in non-solvent system h. ave been studied. The reaction was carried out in an autoclave and the results were evaluated from the viewpoints of a catalytic action on the reaction rate and effects upon the color of polyethylene terephthalate formed by polycondensation from reaction products.
From the experiments on about 100 compounds mostly composed of organic amines and quarternary ammonium salts, we have obtained following results:
(1) The catalytic activity mainly depends on the molecular structure of the catalysts. As to primary, secondary and tertiary amines, (a) the activity increases in following order, primary secondary tertiary; (b) no effect on the catalytic activity due to c4rboncihain length i s observed; (c) n-alkyl amines are more effective than corresponding branched alkyl amines; (d) introduction of OH-group on an alkyl radical reduces the cqtalytic effect. As to quarternary ammonium salts, (a)existence of CH3 gro in the compound shows lower catalytic effect; (b)the difference of catalytic effect due to the kind of a: nions(OH Cr, B, Int) is scarecely observed.
(2) eterocyclic compounds do not show superior efect,
(3) Concerning organic a mines, no correlation between their basicity (degree of strength of bases) and the catalytic activity is observed.
(4) Trialkylamines and quarternary ammonium salts have proved excellent catalysts for this reactlon.

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The mass spectra of 4-methoxy (6), 3, 4-dimethoxy (halkendin) (1), 4-ethoxy-3-methoxy (12) furo(3, 2: 6, 7)coumarin, and their 2, 3 dihydrocompounds (7, 8, 13) are recorded in Figs.1, 3, 4, 6 and 7. The fragmentation is discussed on the basis of high resolution data, metastable ion evidences, and deuterium labelling studies (Tables ltv8 and Figs.2, 5, 9 and 10).
The spectrum of halkendin (Z) shows a major breakdown pathway involving initial loss of a methyl radical from Cs methoxy group followed by expulsion of CQ, then successive loss of CO, CH3(C4), and CO(Fig.5).4-Ethoxycoumarin 12 shows Ioss of ethylene om C, side chain giving an ion m/e 232 whose further fragmentation is very similar to that of 4-hydroxycoumarin derivatives (Fig.10). op.
It is shown that significant structural information can be obtained from the mass spectra of 3, 4-dialkoxyfurocoumarins.

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The infrared spectra of deuterated cellulose and IV Prepared from I and in the 3 region have been reported by Mann and Marrinann who attempted to distinguish the and they were named I and V and N rr.
Iand li gave: nearly the same equatorial pattems of X-ray diffraction, In both of them, however, there were conspicucus difference in the relative intensity ratio, 1(02)(04e), of meridional diffractions. The same was true for IV I and V il. In this paper, these will be discussed.
R was 2/1, 1/2, 1/8 a: nd 213 in 1, E, N I and N ll, respectively. Therefore, I and, I NI and N ll can be distinguished with each other ih meridional X-ray patterns
Despite the chain pac: king in the unit cell seems to be similar between I and H and between N l and IV, their molecular cOnformations may be different.

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It may be of interest to summarize the possible transitions among the different crystalline m di cations f cellulose: 1, , 1, rr, 1V I and N n.
It is recognized that these modifications are classified into two families; cellulose 1 family (1, Iand NI)and cellulose family(, ll and N ll).
In cellulose I family, the transitions among I, I and NI are possible with eachother; the same is true for cellulQse family. Cellulose I family, however, can be transformed into cellulose, but the reverse is not true.
It is considered from these experiments that the chain conformations in cellulose 1 family and in cellulose family are different with eachother, and that the former and latter have bent and bent-twisted type cenformations, respectively.
It is newly recognized that cellulose N i can be tran formed into cellulose 1 by acid hydrolysis.

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Crystalline structures of cellulose triacetates and their saponification pxeducts derived from various crystalline modifications of cellulose were studied by means of X-ray diffraction method. In fibrous acetylation, cellulose I family(l, lll and lV)yields triacetate I and cellulose ll family(ll, lll and lV)yields triacetate ll or mixture of triacetate I and ll. These results show that no clear relationship of crystalline structures between cellulose and triacetate can not be found.
These triacetates, which are derived from cellulose I family and not recrystallized, are saponified to cellu1ose I, while those derived from cellulose ll family are saponified to cellulose ll. It is shown that structural history of two families remains in fibrous acetylation and saponi-fication processes. It is considered, therefore, from these results that the chain conformations in cellulose I family and ll family are different with each other, and in cellulose I family cel1ulose I conformation is more stable on the other hand in ce11ulose ll family, cellulose ll does.
In homogeneously acetylation, all modifications give triacetate ll structures and each of them is saponified to give cellulose ll. It seems that in this acetylation process the chain conformation transforms from cellulose I family to more stable cellulose ll family.

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It was found that 1, 3-dioxolane and tetrahydrofuran were polymerized by some metal acetylacetonates Me(acac)x in the presence of acetyl chloride at O C to give these polymers with a polyether structure(Tables l and 2). The binary system of Fe(acac)8 and acetyl chloride was the most effective while the yield and the reduced visc sities of these polymers were increased with the reaction time(Figs.3, 4and 7). In the polymerization initiated by this initiator system, an induction. period appeared, which was shortened when the nitiator system was aged at O C. From the ESR spectra during the reaction of Fe(acac)3 with acetyl chloride, the production of ferric chloride was confirmed. Accordingly, it was assumed that the polymerization was initiated by an acetyl cation or ferric chloride produced through the reaction of Fe(acac)8 with acetyl chloride.

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The pyrolysis of poly(vinyl chloride)(PVC)containing antimony trioxide(Sb2O3)as an in organic flame retarding agent has been studied The effect of Sb2O3 n t: he flame retardati n and its mechanis of dehydrochlorination has been investigated,
The experimental results presented have lead to the following conclusions.
1) The initial reactio: n of the PVC containi: ng Sb2O3is the oxidation f PVC by Sb2O3, Carbon di xide and carbonyls are formed at 180 C, when the PVC was heated This process was followed by the dehydroch1 rination reaction at 200 C, which is lower than in the case f pVC alone. Above 400 C, the oxidati n of dec mp siti n pr ducts f the PVC takes place. About 485 C, the PVC begi ns to burn,
In these pr cesses, antim ny trichl ride(SbC13)is f rmed by the reacti ns between HCl and Sb, 03 as well as between PVC and Sb203 Apart of Sb2O3 is xidized to Sb2O42)The flame retarding mechanism f Sb2O3 is explained as f 11ws SbC13 f rmed by the it needs heats t fuse above reactions, prevents the temperature of the PVC fro: m rising for r evap rate. Furtherm re, SbC13 gas may be c nsidered t, inhibit the xidati, n f the dec m P siti n pr ducts f the PVC ln the presence f SbC13(17)the activati n energy f PVC t ignite is 23 kcallm 1, which is twice higher than that in the absence, f SbCI3, The igniti n temperatures and the activati n energies f igniti n f b th PVC al ne and PVC containing Sb203 were measured The results are given in the table,
PVC alone PVC contai ing Sb203
1gnition temp 475 C 485 C (20 wt)
Activatin energy 12 kca1/mo1 16, 6kcal/ 1(5 wt)
Flame retarding effect is clear from the table in case of the PVC containing Sb203, 3)Tendency f decrease in a unt f ch1 r benzene and ben ene were bserved t be rather larger in the PVC c ntaining Sb203 than in PVC alone by means of pyrolytic gaschromatography

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The surface acidities of nickel and cobalt sulfates were measured by using. a series of nitr6aniline iridic'slators having very similar structures with the aid of a visible sp. ectrophot-omgtgr The present method may be applicable to the aci dity measurem. ept. of s. trongl golo, red s. opm/i. dEBoth nickel and cobalt Sulfates were found to show maximum acidities when. calciped a-t 3sOoC, fiith is result was in good agreement with that ebtained for nickel. sulfaite by usin. g. Han paett fi-d-ich-i6-rsrm etc. The acirdity m-aximum of nickel sulfate was highgT tban tha t. of coba t. sulfate, gV eVx pueu6 ffrom the diffe rences between the electronegativities of both metal ions and between their catalytic activities already repoxted.

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Thermal decempesition of Na, Mg, K, Ca, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba and Pb formates were investigated by use of gas chromatography and thermogravimetry.
(1) Upon the decompositions of Na, Mg, K, Ca, Mn, Zn, Sr, Cd and Ba fermates, H2, CO and CO2 were formed as the main gaseous products, together with small amounts of CH4, HCHO, HCOOCH3 and CH30H. These organic compounds were formed by secondary reactions from the othetgaseous products under the catalytic actions of the solid products (carbonates or oxides), (2) The deconipositions of Co, Ni, Cu and Pb formates proceeded through main proCess (a)and side process (b).
The molar ratio of MO te M in the products was highest in the case of the decompqsition of Co formate and was about 50%. ln the case of Pb formatei, two kihds of weak catalytic action of solid products were observed, i. e. Pb metal produced autocatalyzed the decomPosition reacti n itself, but, PbO catalyzed the formation of organic compounds except for CH4. How- ever in the other cases, the autocatalysis of metal was pred minantly observed.

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The role of functional grodPs of gel atin to combine with zinc ions was studied by means of polarography and equilibrium dialysis.
Carboxyl, imidazole and amino groups of gelatin were blocked chemieally by esterification, carboxamidomethylation and aoetylation, respectively. Polarography and equilibrium dialysis experiments showed that zinc ions bound less with each modified gelatin than with original gelatin.
If the binding sites were assumed to be imidazole groups, an approximate calculated value for the associatioti constant of zinc-gelatin complex (log K=3, 8 at pH 7.5) was much larger than the first association constant of zinc-imidazole complex.
The result suggests that zinc ions form chelate compound with gelatin.

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The equivalent iconductivities of alkali, alkaline earth, and tetraalkylammonium perchlorateg were mehsured in hexamethylphosphoramide(HMPA). The ionic equivalent conductivities of catiens obtained on the assumption that of the perchlorate ion to be 15, 5 were Li 5.2, Na 5, 8, K+ 6.1 Rb+ 6.1, Cs; 6.4, Ca2 8.6, Sr 8.6, Ba2 8.4, Me4N 7.9, Et N 9.3, Pr. pt 6.8, BuiN.5.9, and Hex, N 4.5. The Stokes law radius of a monovalent cat-ion is smqll-est for Et 4N. The solvation number obtained from the effective ionic radius of Robinson and Stokes is from one to two for a lkali ions and apProximately three for alkaline earth ions.

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During the/ study on a flame retardant. for cellulesic materials, plastics, etc., it has been found that water-insoluble guanylureq, polyphosphate precipitates when an aqueous solution of guanylurea sulfate is added to that of sodium polyphosphate, h, , aying a mean chain length more than 5, and that this substance has a good fiame retardancyt The precipitated guanylurea polyphosPhate was a white fine powder insoluble in most organi solvents and decompbsed at 314to 317oC.
To test the flame reta'rdancy of guanylurea polyphosphate following to JIS A 1321 (Testing Meth' d f, r, mbustibility, fll terna1 ish Material and Pr cedure, f Buildings), was prepared he e Preof paint whic 1 ontains the ame retardant ased, : n. this substance Fro the result of a face test with the paint, it has been con med that guanylurea polyphosphate has not only a good flame retardancy but also the function. to reduce the generation of. smoke.

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High purity TiFs was prepared by the thermal decor sition of arpmonium tetrafluorotitanate(III). TiF3 was prepared: m re easily by this: method than the previdusly rep rted ones. When titanium metal was dissolved in 55 wt% hydrofluoric acid in an argon atmospherc until hydrogen ev 1uti n stoPPed, the dar: k vi let precipitate was formed Ammonium tetrafluorotitanate(III)was formed by the addition of excess ammonium fluoride to the solution containing this precipitate. TiFs was easily prepared by the thermal decomposition of ammonium tetraflueretitanate (III)in a hydrogen or an arg n atmosphere at 600-650 C.
Ammonium tetrafluorotitanate(III)colered yellowish pin: k and oxidized gradually in an air.

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The possibilites of applying the zone-melting technique to a separation of xylene-ev, a'diamine(XDA) isomers were investigated.
The starting sample(f, p.14.0)used in this experiment was a mixture containing about 30fe 50f P-XDA in m-XDA.
In a glass tube container of 9 mm 1, D., the zone passages were carried out for 1. v8 times at a fixed zone travel rate of 32 mm/hr in the room kept at 5"C.
After the repetition ef refining operatiens in series, a material of freezing point 62, 1"C was finally obtained, The final product was identified as highly pure p-XDA by compqFing-!tS'infraied spectrum and freezin- @point with those of an auihehtic sample ef prXDA, The yield of the final product in the last operation was 18%.
t Studies on Zone Melting for Purification ef Organic Cempeund. IV.

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