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Yoshio Toshiyasu, Ryoichi Fujishiro
1973 Volume 1973 Issue 3 Pages
429-433
Published: March 10, 1973
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The electric dipole moments of a, to-qlkanediol monomethyl ethers (mME) and dimethyl ethers (dME) such as HO(CH2)nOCHs and CHsO(CH2)nOCH3, respectively, (n being varied from 2 toli 5)were measured in cyc1 hexane, benzene and dixane solutions at 25 0.02 . The observed values for diol mME in cyclohexane and benzene increased with increasing n until n r 4, then' Pfor n :5, while these for diol dME showed the minimum value at n=3 (of. Fig. 2). These results lead to the conclusion that for the n=3 and 4 the conformations forming intramolecular hydrogen bond for diol mME contribute appreciably to t he observed values. The dipole moments for 1, 5-pentanediol mME in all solvents agreed with those calculated by assuming that all the internal rotations are free. The dipole moments of ethyleneglycol mM E suggests the exsistense of the intramolecular hydrogen bond. Population analysis of the intramolecular hydrogen bonded and nonbonded species in various solution is also given (of. Tabie 5).
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Yoshio Toshiyasu, Ryoichi Fujishiro
1973 Volume 1973 Issue 3 Pages
434-438
Published: March 10, 1973
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The electric dipole moments of 2-haloethanols, X(CH2)20H (X :F, C1, Br and 1) and 2-haloethyi methyl ethers, X(CH2)20CH3 (X=Cl and Br), were measured in solvents sueh as cYclohexane, benzene and dioxane at 25 O.02 e C. The obserVed values for 2-haloethanols increased in t he order cyclohexane benzenedxane(Table 2). This result is explained in term of the difference of the population of the intng, molecular hydrogen bonded conformation i n each solution, This conformation is GG type and has a small dipole moment (of. Table 6).
Therefore the fraction of the intramolecular hydrogen bonded conformation prese.nt i n solution i nc re as es in the or de r, d i ox an e b en ze ne c yc lo he xa ne (c f.T ab le 7),
I The observed values of 2-haloethyl methyl ethers in all solvents agreed with those calculated by assuming that all the internal rotation were free.
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Hiroyasu Nomura, Yasuyuki Sakakura, Yutaka Miyahara
1973 Volume 1973 Issue 3 Pages
438-442
Published: March 10, 1973
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The mean activity coefficients of tetraalkylammonium salts in aqueous solutions at were determined by the freezing-point depression method for a concentration range O, 005 mol/1 to O.7 molll.
The mean activity coecients, of these salts were smaller, in genera1, than the values obtained by Lindenbaum et al. at 25 . Especially for (C2Hs)tNli (n-C4Hg)4NBr and (n-Cs Hg) NI, the r values weire smaller than the values estimated by the limiting-law of Debye-Httckel theory for a low concentTation range.
The values for chlorides increased with the size of cation. The bromides and iodides, however, showed the reverse trends.
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Juziro Nishijo, Isamu Imanishi, Genzo Hashizume, Toshio Kinugasa
1973 Volume 1973 Issue 3 Pages
442-445
Published: March 10, 1973
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SOIid complex formation of oxal ie acid with several a-ami no acids was studied by usi ng an X-ray diffractometer, a R i ltfrared spectrometer and a differential thermobalance a Ralyser.
Oxalic acid forms enly o ne ki nd of complex with dlnt-ala nine, dl-nerleucine or dl-leucine i n a molar ratio of 1:1, while it ferms two kinds of complexes with glyei qe, dl-a-ami Robutylic aeid, dl-val i ne. dl-norvaline o r dl-isoleuci ne i n molar ratios of 1:1 a nd 1:2. lt was presurned that the formation of the cemplexes was promoted by proten-transfer from the carboxyl group in oxalic aeid to the ca rboxyl ion of amino aeid i n t he case of 1:1 complex and by the intermolecular hydrogeR bond between two hydregen atoms of t h e carboxyl groups i R oxalic acid a nd t he carboxyl ions ef t wo molecules of ami no acid i lt t he case of 1:2 complex.
The difference i n com plex formatioA amoRg a-ami nO acids is suppostxl to resu l t from the steric request of a-ami no acid, although it can hardly be explai ned enly by the size of the alkyi group at a-position.
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Tadaatsu Ido, Noriyoshi Morita
1973 Volume 1973 Issue 3 Pages
446-453
Published: March 10, 1973
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Effects of foriT ed and pre-mixed water on the dehydratioN rate of ethanol over alumina at 250 C dil l adso ption of water and ethan 1 n the catalyst near the reace perature were.
No appreciable.ethylene is.produced at 250 C. The rate of production of ether inereased with .lpc uantitatively in Fig 7and the maxi-m f the catalytic activity is
In yiew .gfA.these.characte; istics, the 1eaction scheme was assumed as in Table 6 and the rate
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Taiseki Kunugi, Tetsuo Kono, Yoshiyuki Shinohara
1973 Volume 1973 Issue 3 Pages
454-458
Published: March 10, 1973
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Oxidative esteriqation reactions of methano1, ethano1, 1-propano1, 2-propano1, 1-butanol, 2-butan 1, cyc 1hexan 1 and benzyl a lch 1 were investigated in liquid phase And the reactins falch1s(methan1, 1-pr pan 1, 2-pr pan -butan61, 2-butan 1 benzyl alch 11- ctan l and cyc1. hexan 1)with acetaldehyde and th sef aldehydes(acetaldehyde pr pi naldehyde acr 1eibutyraldehyde, isbutyraldehyde, methacr 1ein and benzaldehyde)with methan1 were alsinvestu- gat6d.
The corresponding esters, aldehydes or ketones are formed selectively Byproducts are hydrocarbons and carbon dioxide from the oxidative decarbonylation of aldehyde
The r6action course is similar to the gas phase reaction as follows:
R OH RCH20H RCHO- RCOOR
par r 1e+CO2
RCH(OH)R RCOR/
Lower alcohols are readily oxidized to the corresponding esters But in the prese: nce of aldehyde the high reactivity fmethanltfr methyl frmate is hindered by the strng a nity qf alde h y de the actie site palladium The re activity fun satura te daldehydes is considerablylower than that of saturated aldehdes.
The reactivity of alcohols with acetaldehyde is well correlated with Tafts.
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Susumu Okazaki, Motoaki Komata
1973 Volume 1973 Issue 3 Pages
459-463
Published: March 10, 1973
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CH C 3, an intereate the pr ess ep ng CHrC 2qCHx-CHCI is dehydrochlorinated by pyrolysis at fairly:high temp ature. The d ts of this paper are tode emetal 1uo ride to catalyze the dehydroch1 rirtion at owe tempe atand to eud te their activites for the ea
Expeen have bee ed Gut by a or the absene or pesen m2varis m fiuerides. The catalytic acdvity f AF3 is vestigated in deta by cha g oln tempe. rature and pretreatments with Cid. bases and steam.
The results obtained are as fdIows:
1 Tbe dehy k i, lori in the abse Of catalySt proceeds at temperature higher t: ha450 C following the rstoder knetics after so inductiope and the reaction rate oo iven by
=3 93x109 e: -41500/R12A.
F, CrF3d MgFe fod to be aive cat. Amongm2th, Ais the most active as reported previky, and ptes the diehydrochlorimation even at as low as 140
The catalytic activitys deceased by pretreatet wihba matedal or with HCI aHsO at lower temperate OR the other hand, it is ed by pretreatment with Hand HtO, which are known to be protatioage, at higher tempeture. Thus this reaction is to be recom2 as the im2c reaCtion pRomoted by the aCtliC Stte f: Xi by the metal inS w have large ion potential.
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Masahiro Kobayashi, Shigenari Fukuda, Takayasu Sirasaki
1973 Volume 1973 Issue 3 Pages
464-470
Published: March 10, 1973
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Cyclehexene formation in the process of dehydrogenation of cyclohexane and caropn monoxide adsorprtion on palladium-graphite(pd-G)ads6rption on palladium-graphite (Pd-G), ruthenium-graphite (Ru-G) apd rutheniumJsilica. (Ru-SiOa)cataijsts were studied. ln the case of Pd-G catalysts cyclohexene yield eorresponds tg the ayerage valuds of CO-adsorption (Fig. 12). ln the case of RuG, the cataiyst, made by the eation exchange method, shows greater values of cyclohexene yield a nd CO-ad Sorption, than that made by the impregnation method (Table 2), ln the cases of Ru-G apd Ru-SiQs, - both of which yvgre prepareq by exchange method, we determined the initial rates-of forpaqtion of cyc.lo.he ene and bEnzene, and examined the dependence of these rates on the partial pressure oC h. ydrogen or cycloheXane. The reaction orders, obtained from the expongntiai. gxpression of cyelghe.xmen.e. fgrthatien, are -0.8 and 1 1.5 with respect to hydrogen and cyclohexem
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Masatoshi Sugioka, Kazuo Aomura
1973 Volume 1973 Issue 3 Pages
471-476
Published: March 10, 1973
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The catalytic cracking of ethanethiol on various solid cataiysts was investigated by the use of a pulse reactor.
It was found that the active catalysts for the cracking of ethyimercaptane were n"ot only NHiYzeolite, solid phosphoric acid (SPA) and silica-alumina (SA) which have the Br6nsted acid sites, but also A1203 and alkali ion-exchanged zeolites, MeY (Me=Li, Na, K, Rb, Cs) which have scarcely the Br6nsted acid sites, However, the solid bases such as CaO and MgO did Rot-sbo y the activity for the cracking of ethanethiol. The cracking products of ethanethiol on NH Y, SPA, SA and MeY were only ethylene and hydrogen sulfide but, on A1203, the significant am.ouns of diethylsu1de were formed together with ethylene and hydrogen sulfide ether hand the cataiytic cracking of ethylmerhaptane on NHN, SPA, SA and A1203 except MeY were pQis.oneq 6TloT Pyrid ne. The cWatalytic activities of NH4Y and SPA for the crac-kipg of b.oth ethanethioi and ctirriene decreased with the increase of the calcination temperature of the catalysts.
F-rM6iT these result described above, it was concluded that the active sites of NH4Y, SPA anq sxei-fToTi thMe-cracking of ethanethiol are the Bronsted acid sites but the active sites of AhO3 and MeY dier from the Brsted acid siteso Active sites of AkO3 and MeY for the reaction were further discussed.
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Tadaaki Tani
1973 Volume 1973 Issue 3 Pages
477-481
Published: March 10, 1973
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In primitive and redution-sensitized emulsions composed of tabular AgBr grais, spectrally sensiting behavior of infrared-range sensitizi ng dyes thiadicarbocyanine (1) a nd thiaricqrbocya ni.pe (2) wasVcompared with that of a desensitizing dye phenosafranine (8). 4 a.nd-L(2) spectra11y sS iprim-itive emulsion, whereas (3) did not. Reduction sensitization enabled (8) tg spe-ctrqliy ensitize, Man the degree of its spectral sensitization increased with increasing degree of reductioq ensitizaiion. On theY other hand, reduction sensitization did not improve the degree of spectra1.ensitization by (1) and (2). Since it is known t hat redetion sensitization brings ab, diout pos.itAi vgole tra ps into silver halidorogans, the above-stated results are, thought to supportble letrorf transfer mechanism, according to which the reason Why (3) ean not spectrally sensitize rises from the rapid transfer of positive holes from (3) in the excited stated to silver halidel hdreas the rapidny transfer of positive holes does not take place from (1) and (2) in the excited tate to silver halides.
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Nagaaki TAKEMOTO
1973 Volume 1973 Issue 3 Pages
482-486
Published: March 10, 1973
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The author studied on phenomena ocurred in the interfacial layer in desalting side of anion excha nge membrane in sodium and potassium hydrogen carbonates electrodialysis. The Schlieren.Diagonal method, previously reported, was employed for observation of the interfacial layer. The decomposition of hydrogen carbonate ion (carbonate decomposition) similar to the water decomposi.tion, HCO3-.HCO32-, has been suggested to occur by the auther, Differences of the state of the interfacial layer between in the water decomposition and in the carbonate decomposition were studied in this paper. The following results were obtained:
(1) There was a state of the interfacial layer obviously distinguishable fromones at both normal and water decomposition conditions at the condition between them. At the condition, the carbonate decomposition seemed to occur(Fig.2and 5).
(2)When the carbonate decomposition occurred, oncentration distribution in the interfacial layer became linear, where small but quick changes were observed (Fig.2and 5).
(3)States of the interfaciaUayer of an anion exchange membrane ih hydrogen carbonates solutions apPeared similar to that of a cation exchange membrane in sodium chloride solution in the foration process of the interfacial layer and in the befavior at the water decomposition. It seemed to be owing to the difference in the transport numbers of solute ions in each solutions (Fig 2, 3a d.5).
(4)For a membrane without treat ment for giving low permeability to divalent anions(M-1), abreak point in current, voltage relation was observed at the beginning of the water decomposition.For aembrane with this treatment(M-), however, two break points corresponding to both the carbonate and the water idecemposition were observed(Fig.1and 4).
(5) Analytical data of transfered quantity of total carbonates seemed also to proveoccurrence of the carbonate decomposition at conditions mentioned above(Table 1).
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Nobuatsu WATANABE, Hiroyasu TAKENAKA, Masayuki TAKASHIMA
1973 Volume 1973 Issue 3 Pages
487-490
Published: March 10, 1973
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The adsorption of fluorine on graphite powder has been studied in a temperature range from -78 Oesi2gOnOeedCfoarnaugtrinPeregssag.reS UP tO 160MMHg by a volumeric method using an appsaratus speciauy
The adsorption isotherms showecl t hat the adsorption increased with pressure ana decreased with temperature, and that it was irreversible and the adsorbed fluorine on the graphite sample was not desorbed by isothermal evacuation.
The potassium iodide solution was oxidized to iodine by the adsorption prQducts. This means that the bond energy between adsorbed fluorine and carbon atoms on the grctphite surface would not be so strong as C-F covalent, bond in fluorocarbon.
The X-ray diffraction patterns showed that t he i nterlayer strueture of gfaphite surface was slightly strained by the interaction of fluorine atoms with x electrons of carbon atoms,
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Ryoko MATSUZAKI, Atsuko SOFUE, Yuzo SAEKI
1973 Volume 1973 Issue 3 Pages
491-495
Published: March 10, 1973
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The phase transition of Bi203 prepared by thermal decomppsitions of Bi(NO3)3 5 H20, (BiO)2COs, and basic bismuth nitrate under various conditions was examined by differential thermal and high temperature X-ray analyses,
On heating ct-Bi20s, it transformed to 6-Bi203 at 731 4 C. When a-Bi203 was heated up to a temperature below the melting point before cooling, a temperature at which the phase transition of Bi203 on cooling changes from the 5.a transition to the 6- P- a transition was 760N780 C.When the 6- a transition occurred, the transition temperature was 715.v 6600C. When the 6.P .cr transition occurred, the transition temperature of a- P was about 6500C, and the transitien temperature of P.a was 570iv540 C. When diBi203 was heated up to 860 C, a temperature higher than the melting point, before cooling, the melt.6- P. a transition occurred. The transition temperature of S.P was about 635 C, and the transition temperature of P- a was 534 v 470 C. As mentioned above, the temperature at which the phase transition on cooling changes from the 6-.a to the 6- P.a, and the transition temperatures Qf 6 and - a vary with the the of preparin Bi0,
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Yoshiyuki HIRASHIMA, Jiro SHIOKAWA
1973 Volume 1973 Issue 3 Pages
496-499
Published: March 10, 1973
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Extraction of raSe earth elements from bastnasite RFCO3 by mineral acids was studied.
DTA and TGA curves show that the thermal decomposition of bastnasite starts at about 400 .The decomposition is accompanied with weight loss, and the rate is proportional to 1/2 power of the concentration of the undecomposed carbonate. According to the X-ray diffraction patterns, the crystal structure is transformed from a hexagonal lattice α=7.19A, o=9.81 A;RFCO to a cubic one α=5.57A RFO by thermal decomposition. Corresponding to it, the absorption bad 870cm of CO32-disappears in IR spectra.
The bumed bastnasite, which had been decomposed by pre.heating, was more easily decomposed by hydrochloric acid than crude bastnasite. Heating of bastnasite at temperature above 500 for lhour gave better result in acid extraction of rare earth elements. The yields of acid extraction of rare earth elements. The yields of acid extraction increased by the elevation of reaction tempe.rature and amounts of acids used. In this study, extraction into hydrochloric 12 nitric16 N and sulfuric18 Nacid was tested. Nitric acid could be used Without any serious trouble. However, some trouble appeared when hydrochloricor sulfuric acid was used residue was ot easlted off in the case of HCI extraction, and solid product formed in the treatrpn.t interfered with the maintenance of a constant condition in the case of H2SO4 extraction. With regard to the yields of rare earth elements, nitric acid extraction gave the best result amo ng the three mineral acids.
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Meisetsu KAJIWARA, Hajime SAITO
1973 Volume 1973 Issue 3 Pages
500-505
Published: March 10, 1973
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Chlorine substitution reactions of phosphenitrilic chloride trimer (PNCi2)3 with 2, 3 or 4-HOH2CC6HsONa and 2-NaOH2CCsHtONa were carried out i n dioxane solvent under various experimental conditions. All those reactions were completed in 40 N 200 minutes in the temperature range from 60 to 103 e C. The chemical shifts of P atom were measured by 3iP-NMR spectra of P3N3C13(2-HOH2CCGHtO)3 (1), P3N3C13(3-HOH2CC6HP)3 (2) and P3N3C14(4-HOH20c6HP)2 (3).The 3iP-NMR spectra showed that the structure of (1), (2) or (3) was non-geminai or geminal pattern respectively. Water vapor, hydrogen chloride and formaldehyde were detected by gas chromatography and plastic polymers were obtained when (1), (2), P3NgC13(4-HOH2CCgHsO)3 (4), P3N3(2-HOH20c6H O)6 (5), P3N3(3-HOH2CC6HP)6 (6) and P3N3(4-HOH2CC6HsO)6 (7) were heated in the temperature range from 150 to 250 C. On the other hand, ring cleavage reaction occurred and polymers were obtained when P3N3Cls(2-OH2CCsHsO) (8) and P3NsCh(2-OH2CCs H40)2(9) were heated in the temperature range from 150 to 200C, but no polymer was obtained with P3N3(2-OH2CC6H40)3. Those polymers were stable tpward water. lt was found from TG that the polymer obtained from (8) was more stable against thermal degradation than other poiymer.The values of resistivity of films formed when (1), (8) were heated at about 300 C for 2 miRutes was 1 N 10 10i 3 st-cm.
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Masumi USIO, Yoshihiro SUMIYOSHI
1973 Volume 1973 Issue 3 Pages
506-513
Published: March 10, 1973
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The weight i ncrease rate (AG) and growth rate of each plane of synthetic emerald single crystal were studied in respect to growth time.
Three or six parts by weight Qf V20s to one part of nutrient containing 5.0 to 1.25 wt% Cr20s were charged in a 400 ml platinum crucible with the aid of a baMe plate. Natural baryl single crystals were used as the seed and the nutrient, Runs were made at about 10500C with a constant temperature. Temperature difference between the seed and the nutrient was 14N15 eC.
Glassy phase formed after the initial equilibrating period of about 5 days, and increased with the growth time. But the glassy phase was not removed from the surface of theelt. Evapo ration rate for the V20s flux at 10500C was about 2 g/day.
The rate of weight i ncrease of synthetic emerald was decreased greatly with the growth time until 10 days, and was cons, tant after 20 days,
The observed growth rates for eaeh plane of synthetic emerald singie crystals were in the folowing order,
c(OOOI) a(n20) m(1010).
The growth rate of c-plane was about 3 to 6 times larger than that of a-and m-planes. The growth rate of each plane was smoothly decreased with time.
For a constant temperature difference, the growth rate of each plane was greater for a crystal that had a higher seed temperature.
In case of 1.25 wt O/o Cr203 dopant to the nutrient, synthetic emerald sing1e crystals colored slightly deep-green. lt was desirable to reduce the amount of dopants less than the above value for synthesis of a transparent green emerald single crystal.
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Ryozo NAKAGAWA
1973 Volume 1973 Issue 3 Pages
514-518
Published: March 10, 1973
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Amethod for the determination of zinc, 1ead and cadmium in hot spring waters by atomic absorption spectrometry has been studied The instrument used was Shimadzu Multichannel Atomic Absorption-Flame Spectrometer, Model MAF-1 The sensitivity obtained by means of the stabilization of electric power and the scale expansion of the recoder readings was sohigh that the sample s 1utions were directly at mized int the acetylene-air ame
The condition recommended for the determinatio:n of zinc, 1ead and cadmium were as follows, wavelength;2139 A, 2170 A a:nd 2288 A, ho110w cathode lamp current;6mA 8mA and 6 mA slit width; 0.05 mm, 0.10 mm and O.05 mm, acetylene pressure;0 2kg/ cm2 0 2kg/ cm2 and O 2kg/ cm2, air pressure;1.4 kg/ cm2, 1.4 kg/ cm2 and 1 4 kg/ cm2 beam p slti n;17 mm 16 mm and 20mm, respectively.
The presence of aids and coexisting elements did not iRterfere, except a large amount of silicon for zin. This interference could be eliminated through an addition of calcium or lanthanum to the sample solution.
The detection limits, determined by means of respective calibration curves, were Zn O.005 ppm, Pb O.Ol ppm and Cd O.OOI C. The method was applied to the determination of the three elements in various types of hot spring waters and the results were satisfactorily coincident with those obtained by other methods.
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Toshihisa MARUTA, Tsugio TAKEUCHI
1973 Volume 1973 Issue 3 Pages
518-520
Published: March 10, 1973
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The interference of iron on atomic absorption of molybdenum and its elimination were investigated for a determination of01ybdenum in steel using a nitrous oxide-acetylene flame,
Iron caused the prominent interference with the molybdenum absorption. The molybdenum absorption was enhanced, it became constant i n various fiame onditions irrespective of irop c-oncentration, provided that the solution containing molybdenum and iron was heated with hydro xylamine hYdrochloride before spraying into the flame.Hydrazine suJfate, isodiu.m sglijtg andu nietailic zific were tested for the reduction of iron and the constant absorption of molybdenum was given in the fuel-lean fiame. ln the fuel-rich flame, the rpolybdenum.absorpti.op was ghtly decrclEised by the elevation of iron concentration. The effects of iron on the molybdenum absorp, tion becamr constant in 0.05 mol/ I phosphoric acid solution, but enhancement effect was lower than that of hydroxylamine hydrochloride.
method. The sample was de60mposed with hydrochloric acid and nitric acid, followed by heatinge, ayhoe standard values. The coe ice nt of variations was about 2%.
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Katsuyoshi SHIBATA, Taiiti OKADA, Mitsuyosi KAWANISI
1973 Volume 1973 Issue 3 Pages
521-526
Published: March 10, 1973
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Irradiation of 2-cyclohexenyl acetate dissolved in acetic acid and xylene gives a mixture of cis- and trans-i, 3-cyclohexanediol diacetates (1:1) in 70% yield. Similarly a mixture of cis- and trans-i, 4-cyclohexanediol diacetates (1:1) is obtained from 3-cyclohexenyl acetate. No structural isomers have been isolated in both cases. The incorporation of carboxylic acids of higher or bulkier alkyl group tends to prefer the trans adducts. The similar reaction of cycloheptenyl acetates requires the presence of concentrated sulfuric acid to give only poor yields of adduts. Possible explanations of given.
The fact that acyloxy, hydroxy or methoxy groups apparently control the direction of addition, suggests that oxygen atom these groups plays an important role by forming four-, six or seven-membered transition states in the protonation step.
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Kiyonori SHINODA, Koji KONNO
1973 Volume 1973 Issue 3 Pages
527-531
Published: March 10, 1973
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It was found that vinyl chloride (VC) was converted into chloroacetyl chloride by photooxidation in the presence of chlorine. The reaction was carried out under various conditions in order to find the optimum conditions for this reaction and to elucidate the reaction mechanisms. The experimental results were explained by the chain reaction mechanism involving 1, 2dichloroethyl radical.
The results obtained were summarized as follows.
(1) The reactions were effectively initiated by light at 330 N 350 nm.
(2) The optimum reaction temperature was 50 N 60 eC.
(3) In the case of a stoichiometric 1:1:0.5 molar ratio of VC:C12:02, chloroacetyl chloride was obtained i n good yield.
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Kiyonori SHINODA, Koji KONNO
1973 Volume 1973 Issue 3 Pages
531-536
Published: March 10, 1973
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As vinyl chloride was converted i nto chloroacetyl chloride by mean of photooxidation in the presence of chlorine, 1, 2-dichloroethane(EDC) was also expected t-o be oxidized thro-ugh- 1, 2-aichloroethyl radical which could also be formed by abstracting a hydrogen atom from EDC.
The present paper is concerned mainly with product distribution under the various reation coRditiens and kinetics of the photochemical oxidation of EDC and 1, 1, 2-trichloroethane sen-sitized by chlorine. The findings led to a conciusion that 1, 1, 2-trichloroethane is formed via vinyl chloride and EDC, and the formation of chloroacetyl chloride was formulated as follpws.
CH CIC HCl C H2 : CH C -=1 12, CH2CICCIg
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Kiyonori SHINODA
1973 Volume 1973 Issue 3 Pages
536-541
Published: March 10, 1973
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ln the chlorine-sensitized photooxidation, chSoroethanes and chloroethylenes are chlorinated owing to the reactivity of ehiorine.
PreMsent paper is concerned with the effect of the Structure on this competitive reaction of chlorine and oxygen, The more Substituted with chiorine atoms, the faster the rate of oxidatien compared with that of chlorination. Relative reactivity was affected remarkably by the polar nature of the Substituent,
Judging from the structure of the oxidation productS, CHsCICHCI, CHsCICCIs and CHCIsCCI2were MpnaaS the radical intermediates which were formed by addition of a chlorine atom to vinyS chioride, 1, 1-dich1oroethylene and trichloroethylene reSpectively.
Trichioromethyl compoundS, such aS CCIgCHs and CCIsCH2Cl, were converted into unexpected aid ch1orideS. The results could be acounted for by isomerization of radicaE intermediates.
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Kiyonori SHINODA
1973 Volume 1973 Issue 3 Pages
542-546
Published: March 10, 1973
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The effect of the structure on the rate of photooxidation in the presence of chlotine was i nvestigated by carring out the competitive reactions with several different chloroethanes and chloroethylenes.
The experimental results showed the decreasing reactivity of chloroethanes in the order:CH3CHCIg-CH2CICH2Cl-CH2CICHC12-CHC12CHC12-CC13CHC12-CC13CH2Cl-CH3CCIs, The reactivity of chloroethylenes was in rhe order: CH2:CC12-CHCI:CC12-CCh:CC12-t-CHCI:CHCI-c-CHCI:CHCI.
A linear free-energy relationship was found to exist between the reactivities of chloroethanes and Tafts 6 constants. pvalues for the substituent(reaction site)-CH2Cl and -CHCIa were -O.99 and -0.72 respectively,
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Kazumasa OSHITA, Eturo MAEKAWA
1973 Volume 1973 Issue 3 Pages
547-551
Published: March 10, 1973
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The o-hydroxy azo compounds of homophthalimide such as o-hydroxy-phenylazo-homophthalimide (HPAH), 2-hydroxy-1-naphthylazo-homophthalimide (HNAH) and 2-hydroxy-4-sulfo-1-naphthylazo-homophthaiimide (HSNAH) were synthesized by the coupling reactions of diazotized traminophenol, 1, 2-aminonaphthol and 1-amino-2-naphthol-4-sulfonic acid with homophthalimide, respectively. Among them HNAH, HSNAH are new compounds.
The acid dissociation constants of these compounds andthe stability cbnstants of their metal chelates have been deterMined by the spetroscopic method.
The dissociatioR constants of HPAH, HNAH and HSNAH are foundto be PKai=9.70, PKa2=12.25 for HPAH in 40%dioxane-water;pKa8.75, pK=12.55 forHNAH in 40%dioxane-water;PKra2=7.72, PKa3=11.52 for HSNAH i n water at 25C.
Various kinds of metal ions form red colored chelates with HPAH and pi nc coiored chelates with HNAH and HSNAH.
The stability constants of the chelate of HSNAHare found to be 17.54 for Cu, 11.64 for Ni, and 8, 84 for Zn respectively.
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Masakuni KOGURE, Kunito TAKEZONO, Shuya FUJII
1973 Volume 1973 Issue 3 Pages
552-556
Published: March 10, 1973
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The hydrolytic cleavage of dypnone (3) to benzoic acid (A-cleavage reaction) catalyzed by BFs was found to be promoted considerably by the addition of inorga nic acids. Moreover the condensation of (3) was suppressed t o some extent by the addition of 85% H3POi.
Difference in activities of BF3 85% HsPOs complexes and BFg, water complexes for A-cleavage reaction was examined. The rate oHormation of (1) cafalyzed with BF3, 85%H4PO4(BF/(H3PO4+H20)=1(mol/mol)) was about three times faster than with BF3, H20. The former complex was more stable for heat. The order of activity for A-cleavage reaction was as follows;
BFs, 8596 HgPOb BFs, H20 BFs 2(85% HgPO4) BF3, 2H20.
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Takaari YUMOTO, Tatsuo MATSUDA
1973 Volume 1973 Issue 3 Pages
556-562
Published: March 10, 1973
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Cyclic ethers were found to add to tetrachloroethylene with r-ray irradiation and to produece saturated and unsaturated 1:1-adducts which contain CHC12-CC12-and CCI2=QC1-groups, respectively. The effects of does rate, total does, temperature and structure of reactant on the reaction mode were studied.
G valuesof adducts change in the following order:tetrahydrofuran oxetane 1, 3-dioxlane tetrahydropyran p-dioxane.p-Dioxane gives mainly unsaturated 1:1-adduct; on the other hand, 1, 3-dioxolane gives mainly saturated 1;1-adduct. These adducts wereproduced with the reactoin rates independent of the does rate.Apparent activatoin energies are estimated in the cases of some cyclic ethers. The addition reaction of this type was found to proceed with organic peroxide catalysts.
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Nobuo ISHIKAWA, Takayoshi MURAMATSU
1973 Volume 1973 Issue 3 Pages
563-567
Published: March 10, 1973
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o-Phenylenediamine, o-aminophenol, 1, 2- and 1, 8-naphthylenediamine and 1-amino-2-naphthol reacted with hexafluoropropene in dimethylformamide to give 2-(a, B, B, B-tetrafluoroethyl)-benzimidazole (1), -benzoxazole (2), -naphthoimidazole (3), -perimidine (5) and -naphthoxazole (4), respectively. o-Aminobenzylamine also gave a six-membered heterocyclic compound, 2(a, B, B, B-tetrafluoroethyi)dihydroquinazoline (6) by the similar reaction. o-Aminothiophenol, however, did not give a thazole compound, but o-aminophenyl hexafiuropropyl sulfide (7) was obtained.Si nce the nucleophilicity for-hexafluoropropene seems to decrease in theorder ArSH ArNH2 ArOH, ring formation is considered to proceed through the reactive imidoyl fluoride compounds formed by the reaction of the amine group with hexafluoropropene.
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Kaoru FUZIMOTO, Yoshio KOYAMA, Taiseki KUNUGI
1973 Volume 1973 Issue 3 Pages
567-572
Published: March 10, 1973
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N-Butenes were oxidatively dehydrogenated to 1, 3-butadiene in vapor pha e over supported metallic palladium catalysts. The effective temperature range of the reactipn was about 140 to 200C. Major by-products were n-butene isomers small amount of carbon, dioxide and methyl vinyl ketone. AEI n-butene isomersyielded 1, 3-butadiene by this reaction. The order of reactivity was 1-C4Hs trans-2- C4Hs cis- 2-C4Hs. Among several supports, porous glass gave the. best activity, but a of carbon dioxide was als6 formed. When 1 wt oPdonr alumina catalyss was eT at 170 C, one pass yield of butadiene and carbon dioxide was 6.7% and O.46 based on 1-butene, respectively.
The oxidative dehydrogeneation proceeded rapidly even in the presence ef small amount of oxygen, while the isoMerezation wassignificantly suppressed by xyge4.The arpognt of 1, 3 bufaVdiehe formed i ncreased with the increase in steam pressure but the isomerized products decreaed.
The active intermediate is believed to be z-allyl complex and the followingreaction scheme is proposed.
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Sei-Ichiro IMAMURA, Kimihisa FUKUMOTO, Hiroshi TERANISHI, Yoshinobu TA ...
1973 Volume 1973 Issue 3 Pages
573-578
Published: March 10, 1973
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The decomposition of umyl hydroperoxide was carried out i n pyridi ne usi ng copper catalysts.
When a cuprous sait was used, the reaction proceeded without any induction period at OC. The rate expression, -d(EHPO)/dt=k(Cu)0.93(HPO)1.00, was obtained and, it was in good agreement with the assn mechanism that the reaction was irri tiated by the cuprous species, When a cupric salt was used, induction period appeared even at 40C, This inductioq, period, disa, ppeare, dby the addition of such compounds as reducihg agents or radicai initia, tors which, educed cupric silt to cuprous state, and was prolonged by adding oxidizing agents which oxidize cuprous to cuprig state, Bhsed on these findings it appears that cuprous species is more active than cupric one and the transformation from cupric to cuprous state occures during the induction period, Under our experimental conditions cumyl hydroperoxide exhibited adequase ithgrmal, stability, There, fore the cubrous species can not be formed during the ipduc tion, period, throughthe reaction between cubric salt and the intermediate radicals formgd by the thermal decompositio4n of hydroperoxied, The possibility of the direct decompositionof cumyl hydroperoxide by cupric salt during the induction Period can not yet beruled out.
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Saburo NAKANISHI, Mikio TAKAHASHI, Futoru YOSHIMURA
1973 Volume 1973 Issue 3 Pages
579-583
Published: March 10, 1973
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Some alkanes were sulforiated with SO3 diluted with air. The produced sulfonic acids seemed to be a mixture of alkenedisulfonic acids, dihydroxy-alkanedisulfonic acids and disulfato-alkanedisulfonic acids. ln these products, theproportion of alkenedisulfonic acid was.independe, nt of the reaction time and temperature, while the proportion of sulfate group increased with increasing timeand temperature.
For the reaction mechanism of alkane with gaseous SO3, it was inferred that SO3 radical reaction might procede rather than ionic one.
From the comparison of desulfenated products from the produced sulfonic acids with those of known sulfonic acids, it was confirmed that the number of carbons ih produced sulfonic acids which contained double bond or hydroxy group was the same as that in original alkanes.
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Tomomi OKAZAKI, Akio OHSUKA, Munio KOTAKE
1973 Volume 1973 Issue 3 Pages
584-589
Published: March 10, 1973
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Neutral components of S. altissima L. roots were repeatedly chromatographed on silica gel to give four oily bitter principles and two crystalline bitter principies. These six compounds have an outstanding strutural feature in common, a B-substituted B-butenolide ring (IR) 1785, 1750, 1645cm-1, 54.65(2 H, d), 5.72(I H, bs).
The hydrolysis of the simplest compound, solidagolactone (7) (CacH3eO2, bp 160-170 C/O.007mmHg, la D -73.4) gave aldehyde-carboxyiic acid (17), which was reduced by the Huang-Minlon method and methylated with diazomethaneto give methyl ester (18) (Eal D -44.70).(18) was identical with methyl dihydrokblavenate (20) (aD -32.6) derived from kolavenic acid (1). Based on the above chemica1 evidences and the spectral properties of derivatives, the structure (7) wasdetermined.
In the other four compounds, solidagolactone II(8), III(9), IV(10)(C2H3003, mp 134)and V(11) (C2 g H2gO3 mp 105-106C), the presenee of substituentsat C(G) was revealed in NIVIIil data, compared to those of the corresponding coinpounds of kolavenate series. Spectral data allow assignment of provisionalstructure (12) to the remaining compound, solidagolactone VI.
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Akio OHSUKA, Shoichi KUSUMOTO, Munio KOTAKE
1973 Volume 1973 Issue 3 Pages
590-594
Published: March 10, 1973
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For the acidic. bitter principles (solidagonic acid (3), 6-ange1oyloxykolavenic acid U5, and 6-tigloyloxykolavenic acid (16)) of S. altissima, the stereostructures of t he oxygen-substituents in the ring Bwere determined. ln the NM R spectra of diel (5) and 7-epidiol (11) derived from (3), the half-band widths of the signals of c-hydrogens were 9 Hz and 23 Hz, respectively therefore, diol (5) has an axial hydroxyl group at C(7). This estimation was supported by thesolvent Jeffect of the signals of C(5) and C(9)-methyl groups. Similarly, in theNMR spectra of diol monoacetate (Z8) and 6-epidiol monoacetate (22) derived from(15) and (16), the half-band widths of the signals of the C(6)-hydrogens were 6 Hzand 20 Hz, respectively. Consequently, (15) and (16) have the axial okygeh-substituents at C(6).
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Akinori SUEOKA, Jisuke HAYASHI, Sadayoshi WATANABE
1973 Volume 1973 Issue 3 Pages
594-602
Published: March 10, 1973
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Differences between native cellulose I and the three kinds of regenerated 6elhilose I which obtained from celhilose I, cellulose triacetate and cellulose trinitrate ware investigated.
It is found that there is the distinct difference betweeen na tive cellulose I and each regenerated cellulose I, which ispossible te transform by heat treatment with glycerol to cellulose lvi, but the former is impossible. As indicated from the equatoriai Xmray diffractograms of regenerated eelluiose I, the 2e a ngles of(002) are O.4 lower as compared with native cellulose I.On the other hand, the profiles of their infrared spectra show the differerences espec, i ally in OH strething and 1300-1400 cm-1 region, and this is considered to arise from the differences in the intermolecular hydrogen bond system.
It is defined by these experiments that regenerated cellulose I is a metastable cryStalline modification, and it is named cellulose I in contrast with cellulose I of native cellulose.
The average degree of pQlymerization is distinguished between cellulose I and I' the fermer is 200 glucose units and thelatter is 80. lt is shown by various transfer reactions that cellulose I' isclassified into cellulose I family.
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Osamu OHARA, Chuji ASO, Toyoki KUNITAKE
1973 Volume 1973 Issue 3 Pages
602-610
Published: March 10, 1973
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Radical copolymerizationsof spiro(2, 4)hepta-4, 6-diene(SHD)and spironona-1o3-diene(SND) were carried out.They gave only Diels-Alder adducts when maleic anhydride was used as comonomer, and styrene homopolymer was obtained in theprefenpe of SHD and SND. On the comonomer, other handl true copolymers viere formed when acrylonitrile(AN) and rnethacrylonitrile MAN were used as comonomers, andthe following reactivity ratios were obtained.
Although the radical reactivity of SHD monomer did not differ much from that of SND monomer, the structuresof these whits in copolymers were quite different. The SND unit was formed bytheconventional 1, 2- and 1, 4-additiens, while the SHD unit mainly eonsisted of the structures which were formed by the opening of the cyclopropyl ring.The structure of the SHD llnit varied slightly with comonomers. This result was discussedon the basis of the competitive monomer addition and rearrangement of the growing SHD radical.
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Bunzo KAMO, Nobuharu SUZUKI, Koji OGAWA, Shijo FURUSAWA
1973 Volume 1973 Issue 3 Pages
610-617
Published: March 10, 1973
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5-Methyl-2, 3-dihydrofuran(MDHF) was polymerized in toluene at low temperature by organometallic compounds(e.g. Al(C2Hs)2Ci), and the microstructure of high polymer obtained was studied by NMR.
The methyl ethyl ketone-insoluble part in the polymer has not been obtained in the crystalline state till now, .but was found to be stereospecific. A triplet due to a-methyl protons with different chemical configurations may be assigned to di-isotactic, heterotactic, and di-syndiotactic with increasing magnetic field. A neariy linear relationship between the Qptical density ratio D1372/D1360 in polymer and the di-syndiotacticity was observed, The conditiQns for obtaining poly-MDHF with high stereospeificity using Ziegler cataiysr are discussed.
The poiymerizatipn in the presence of asymmetric cationic catalysts ffom Al(C2Hs)2Cl apd P-phenyialanine led to polymerS having optical activity. The optidalactivity shown by the polymer indicates the presence of chains an erythro-di-isotactic structure.
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Takeshi ENDO, Takao MOGAMI, Makoto OKAWARA
1973 Volume 1973 Issue 3 Pages
617-621
Published: March 10, 1973
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Hydrolysis of N-vinyl-2-oxazolidone(NVOx) was studied in the presence of various acids at the different pH. Solvent effects on the hydrolysis were investigated. lt was concluded that there is a large contribution of hydrophobic or hydrogen bonding interaction between NVOx and acids.The rate of hydroiysis isproportional to t he first order of NVOx and acids concentration, respectively. Activation energies and activation entropy change in this hydrolysis were ca.16kcal/mol and -24 N-27 e.u., respectively.
Further, hydrolysis of N-vinylpyrrolidone(NVPy) was examined and it was found that the rate of hydrolysis of NVPy waslarger than NVOx.
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Yoshio TOSHIYASU, Ryoichi FUJISHIRO
1973 Volume 1973 Issue 3 Pages
622-623
Published: March 10, 1973
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The electric dipole moments of w-chloroalkanols, Cl(CH2)nOH (n beingvaried from 3 to 5) were measured in solvents such as cyclohexane, benzene and dioxane at 25 0.02 The observed vaiues of tu-chloroalkanols are considerably iower than the value calculated by assuming that only the i ntramolecular hydrogen bonded conformations contribute to the dipole moment, indieating that t he i ntramo1ecular hydrogen bonded onformations hardly exist. One the hand the values calculated by considering that all the internal rotations are free, are a little higher than the observed values, These differences may be qualitatively explainedby excluding some repulsive conformations.
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Toshiaki NOMURA, Isao ANDO, Toshio NAKAMURA, Sumio KOMATSU
1973 Volume 1973 Issue 3 Pages
624-626
Published: March 10, 1973
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Thiosulfate ion reacts with mercury(II) ethyienediaminetetraacetate (Hg EDTA) to form mixedligand compiex (Hg-EDTAhLS203, colorless). Hg-EDTA-1, iodo mixed-iigand complex of Hg-EDTA, is more stable than the Hg-PC-1, iodo complex of mercury(II)-cresolphthalein complexone (Hg-PC). Thiosulfate ion, therefore, can be titrated with a Hg-EDTA solution using Hg-PC-I complex as an indicator:
Hg-EDTA+S20s=Hg-EDTA-S20s
Hg-PC-1 (pale pink) + Hg-EDTA=Hg-PC (red-violet) + Hg-EDTA-I
The pH of a sample solution was adjusted to 9.0-10.5 with bpffer solution, to which a Hg-PC-1 indicator solution was added. The solution was titrated with a standard Hg-EDTA solution. End point was determined by color change of the solution from pale pink to red-violet.
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Yoshio IMAI, Takeyoshi TAKAHASHI
1973 Volume 1973 Issue 3 Pages
627-629
Published: March 10, 1973
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Phthalic thioanhydride reacted with ise-butylamine, benzylamine, cyclohexylamine, b-aminobenzoic acid, P-aminobenzenesulfoAamide, o-aminobenzamide, and o-phenylenediamine in ethanol at 80C, with the evolution of hydrogen suifide, to afford N-substituted phthalimides in good yields.Phthaloylation of glycine, B-alanine, and o-aminobenzoiacid was also achieved under basic reactions conditions. A probable reaction route is disussed.
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Kazuo KITAMURA, Fumio SHIBATA, Zen-ichi YOSHIDA
1973 Volume 1973 Issue 3 Pages
629-631
Published: March 10, 1973
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Volume term in the disperse dyeing of the heat-setted poly(ethylene terephthalate) fibres was investigated in relation to their fine structure.
The volume term depended not only on the crystallinity but also on the history ofthe fibres.In the case of the samples of same crystalli laity, the volume term increased with the degree of the heat-setting temperatute, and decreased with theamount of the draw ratio. The samples with higher peak inteRsity of small angle X-ray scattering had larger volume term than those with the lower intensity.
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Akio OHSUKA, Shoichi KUSUMOTO, Munio KOTAKE
1973 Volume 1973 Issue 3 Pages
631-632
Published: March 10, 1973
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A new diterpene carboxylic acid methyl ester, methyl dehydrokolavenate (2) (C2iH3202, bR 175N1800C14 nimHg, aD +21), was isolated from the methylated acid fraction of the root of Solidago altissima L. lt has an exocyclic methylene group and two other double bonds. Thg catalytic rection of(2)gave methyl kolavenate(1)and two isomeric dihydro derivatives(3) and (4).
BaSed on the above chemical evidence and the spectral properties, methyl dehydrokolavenate was formulated as (2).
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