Nippon Kagaku Zasshi

(Journal of the Chemical Society of Japan ; Pure Chemistry Section)

Vol. 81, No. 6, pp. 833-986 (1960)

These abstracts are prepared for the benefit of our readers abroad to assist them, to form a

general idea of the contents of the present issue written in -Japanese by respective authors. Readers
are recommended to refer to the tables, the figures, the formulae etc. in the original papers. Editor

Abstracts

tivity is strong when the amount of the added metal is

1. General and Physical Chemistry samll, and is decreased with its increase. In general,
the increase in the catalytic activity is brought about
by increasing both the apparent activation energy and
the frequency factor which are in compensation with
Nippon Kagaku Zasshi, 81, 833-%-836 (1960) each other.
On Sulfate Complexes of Uranium(V1)
by Shigeki MATSUO II. Activity in the Catalytic Hydrogenation of Cyclohexene
The formation constants and the absorption spectra (pp. 842^-847)
of uranyl sulfate complexes have been investigated
In order to confirm whether the results described in
spectrophotometrically. The measurements are performed Report I of this series are obtainable with other sub-
at 25°C, and the ionic strength remained constant at stances, attempt was made on the catalytic hydrogenation
1.00 with sodium perchlorate. The formation constants
of cyclohexene as an example of compounds having an
of 1 : 1 and 1 : 2 complexes were evaluated to be 65±2
ethylenic bond. As in the acse of nitrobenzene, maxi-
and 3 ± 0.4, respectively. The values obtained by
mum activity is attainable by the proper choice of the
Ahrland were in accord with the present values sub-
temperature and the time of leaching alumium-nickel .
stantially. The absorption bands of sulfate complexes
The optimum time of leaching at the same temperature
shifted to longer wavelengths with increasing number
is much longer in the case of nitrobenzene than that of
of complexed sulfate ions, but the spectra of the sulfate
cyclohexene, and thus leaching conditions for attaining
complexes were observed to be similar to that of the
maximum activity are different according to the kind of
uranvl ion.
individual substances to be reduced. In two-component
Research Institute of Mineral Dressing and Metallurgy , Tohoku catalysts the added metal in a small quantity always
University; Sendai-shi, Miyagi, japan acts as a promoter, and transition metals are especially
effective as metals to be added. According to the
electronic theory of Dowden, copper in nickel-copper
series catalysts acts as a poison, but in the present
work copper was found to act rather as a promoter .
Nippon Kagaku Zasshi, 81, 837--.847 (1960)
Research Laboratories, Takeda Pharmaceutical Industries
Study on the Catalytic Activity of Raney Nickel Catalysts . , Ltd; Hi
gashiyodogawa-ku, Osaka, Japan

by Jusaburo ISHIKAWA

I. Activity in the Catalytic Reduction of Nitrobenzene

(pp. 837-^,842)
Nippon Kagaku Zasshi, 81, 847-,•852
In regard to catalysts to be used in the liquid phase The Adsorption of Isoniazid on Cation Exchangers of
reduction of nitrobenzene , experiments were conducted Various Metal Forms
to make clear the catalytic activity in relation to the
leaching conditions of aluminium-nickel alloys with vari- by Akio TSUJI and Keiji SEKIGUCHI*
ous compositions, and the kind and amount of the added
It is known that INAH (Isoniazid) forms chelates
metal in several two-component catalysts . The activity with such divalent cations as Cu2+ , Ni2+; Hg2+, zn2+,
of the catalyst prepared from aluminum-nickel alloy
Co2+, Fe2+. The adsorption of INAH on cation exchan -
depends upon its composition , the temperature and time gers of various metal forms was investigated . It was
of leaching, and therefore a catalyst having strong ac - found that INAH was quantitatively retained o
tivity may be obtained only when these factors are n the
bed of cation exchangers (Dowex-50) of some metal
properly chosen. In two-component catalysts their ac- forms, The elution curves showed that the affinit
y of
 A62 Nippon Kagaku Zasshi Vol. 81 No. 6 (1960)

these cation exchangers to INAH decreased in the order: Nippon Kagaku Zasshi, 81, 855-858 (1960
cu.2Ni2-1->Hg2+H+>Co2+ >Cd2±Zn2+ >Fe2+ > Pb2+ > Infrared Spectra and Intramolecular Hydrogen Bonding in
Mn2+ >A13. This is the same as that of the stability a-Keto and a-Alkoxy Carboxylic Acids
of the chelates with metals as has been reported by E.
by Michinori OKI and Minoru HIROTA
Mellor. . INAH was not adsorbed on Ba, Mg, Ca and
Na-resins. INAH adsorbed on Cu, Ni, Hg, and H-resins The infrared spectra of a number of keto and alkoxy
was not eluted with water, while INAH adsorbed on Co, carboxylic acids in the 3 micron region were measured
Cd, Zn, Fe, Pb, Mn and Al-resins was eluted. The and it was found that the 0-H stretching band has two
adsorption capacity of INAH which proved independent peaks when a proton accepting group (such as carbonyl
of metals amounted to ca. 0.5 m mol. INAH per 1 meq. or alkoxy group) exists at the a-position. The absorp-
H-resin or 1 mol. INAH per 1 mol. divalent ion. The tions at higher frequencies lie between 3550 and 3500
mechanism of the adsorption was discussed on the basis cm.-1 and they are assigned to the 0-H stretching mode
of the infrared spectra, the changes of pH and the of free monomeric acids. The absorptions at lower fre-
adsorption of benzoic acid hydrazid and pyridine on quencies are assigned to the 0-H stretching mode of
the cation exchangers. the internally hydrogen-bonded from, and these absorp-
*National Hygienic Laboratory; Setagaya-ku, Tokyo, Japan tions appear only when a five-membered ring can be
formed by hydrogen bonding.

Department of Chemistry, Faculty of Science, the University of Tokyo;

Bunkyo-ku, Tokyo, Japan

Nippon Kagaku Zasshi, 81, 378 (1960)

Studies on the Polyesters from 19-HydroxyethoxyAromatic
Acid. Ill. The Crystal Structures of Polysters from P-
Hydroxyethoxy Aromatic Acids Nippon Kagaku Zasshi, 81, 858--862 (1960)
Infrared Absorption Spectra of DL-a-Chloro-n-butyric Acid
bY Mikio KOREMATSU* and Sutezo KURIYAMA
and its Related Compounds
The crystal structures of polyesters from 4-(p-hydro-
by Tadao TAKENISHI
xyethoxy) benzoic acid,
Infrared absorption spectra of DL-a-chloro-n-butyric
11 / (Polyester A) acid, deutero-DL-a-chloro-n-butyric acid, sodium DL-a-
0 chloro-n-butyric acid, DL-a-amino-n-butyric acid and DI,-
3-metoxy-4-(p-hydroxyethoxy) benzoic acid a-amino-n-butyric acid hydrochloride have been observed.
Probable assignment has been given to every observed
\oc (polyester B)
0 H3 band, on the bases of the comparison of these spectra.
and their copolyesters (copolyester A : B) have been For DL-a-chloro-n-butyric acid, only one C-Cl stretching
studied by the interpretation of the X-ray diffraction vibration has been observed at 686 cm. -1 in the liquid
patterns given by drawn and heat-set fibers. The fiber state and in the carbon disulfide solution. From this
identity periods. (those parallel to the chain molecules) fact, it has been concluded that this compound exists
were about 15.5 A and they are far less than that re- only in one form, in which C-Cl bond is in the trans
quired for a fully extended planar chain with two position with respect to the C-CH3 bond in the internal
chemical units (19.6 A), the chains have therefore large rotation of the Ca-Cp axis. A discussion has been made
scale zigzag in which each limb contains a number of on the differences in the characteristic frequencies of
atom. Beside those normal patterns in the X-ray dif- the carboxyl group between a-chlorobutyric acid and
fraction photographs given by fibers which are drawn a-aminobutyric acid.
to high ratio and heat-set under high tension, there are The Central Research Laboratory of Ajinomoto Co., Inc.; Kawasaki-
some fairly diffuse diffraction spots which indicate that shi, Kanagawa, Japan
there are the other unit cell whose fiber identity periods
are about 19.0 A, consistent with the fully extended
chain. The unit cells of the polyesters are calculated
by trial and error method, and they are to be monoclinic
with a— 10.80--12.87 A, c=4.72-446A, p Nippon Kagaku Zasshi, 81, 863--870 (1960)
(these are varied with A : B) and b=15.45 15.45 A. Those The Magnetic Study of Nickel Catalyst.
give densities of the crystals (1.359-4.473 g./cc.) which by Kozo UMEMURA
are consistent with the densities of drawn fibers and
estimated value from specific-volume temperature rela- I. The Magnetization Measurement of Nickel Micropowder
tion of the polyesters. (pp. 863---866)
*Research Department , Kokoku Rayon and Pulp Co. Ltd.; Saeki-shi, The magnetization of nickel powder in partially ae
Oita, Japan
composed nickel formate and nickel oxalate was measur
ed at room temperature in the magnetic field of strengti
range from 200 to 1600 Oersteds. The saturation valu(
of magnetization Is, which was obtained by extrapolating
the observed I vs. 1/H curve, was found to be propor
tional to the decomposed amount of nickel. The ap
proach to saturation is expressed by the formula;
 JibsiracigA6 3

1- From the observed magnetization curves, Nippon Kagaku Zasshi, 81, 875--881 (1960)
powder was proved to be of single domain particle. The Structure of Adsorbed Layers at the Interface Mercury—
lower was the decompositon degree, the higher its Surfactant Solution. V
magnetic hardness. At comparatively higher region of
by Keiichi EDA
magnetic field applied, the magnetization curves are
expressed by the formula; //is ---- (1+ PH) where le VIII. Structure of Adsorbed Layers of Cationic Surfac-
is a parameter which is reciprocally proportional to a, tants Which ronize Strongly (pp. 875"--878)
and represents the magnetic hardness of the material.
Differential capacities of the electrical double layer at
the interface mercury/aq. solution of cationic surfactant,
II. The Magnetic Behavior of Nickel Kieselguhr Catalysts dodecyl pyridonium chloride (DPC) and dodecyl trimethyl
(pp. 866"-870) ammonium chloride (DTAC) , were measured by the
impendance bridge method. Sodium chloride or sodium
The magnetization of nickel kieselguhr catalysts whose
sulfate was used as a supporting electrolyte. Two im-
contents of nickel are 26-48% was measured within the
magnetic field range from 100 up to 1800 Oersteds. From portant features observed in the differential capacity vs.
the feature of the observed magnetization curves and voltage curves are as follows. Firstly, at the anodic
also from the fact that the plots of I vs. HIT are in- polarization the cross point or desorption peaks appears
dependent of temperature, the catalysts can be con- at the low concentration of surfactant, DPC or DTAC.
sidered to be superparamagnetic. Observed magnetiza- It was indicated that the cross point which appears in
tion curves can be expressed by the formula; I / the case using sodium chloride as a supporting electro-
lyte is a alternative of the desorption peak. Secondly,
(811)a1 (1+ (PH)a), a=0.86---0.88,
0.86--0.88, where Is is apparent
saturation magnetization, and is obtained by extrapolating the differential capacity at zero or the cathodic polari-
1/I vs. (1/H)' plots. It is proportional to nickel content zation has its minimum value at the intermediate con-
in the catalysts, p is a parameter referring to the size centration, 5x105 N of DPC. At the higher concentra-
of nickel particles. Particle size and its distribution tion the capacity rises with the increase of concentration.
in the catalysts were discussed by comparing the ex- The consideration on this behaviour from the thermody-
perimental results with the Langevin equation. namical point of view suggests the increase of surface
excess with the increase of negative polarization. It may
The Department of Chemistry, University of Osaka Prefecture; Sakai-
be probable that a part of the adsorbed ions is oriented
ski, Osaka, Japan
with the heads toward mercury, resulting the double
layer adsorption.

IX. Structure of the Adsorbed Layer of Dodecyl Amine

Nippon Kagaku Zasshi, 81, 870-.4374 (1960) Chloride (pp. 879---881)
Studies on Porous Structure of Active Carbons. VIII.
The Alternation of Pore-size Distribution Differential capacities of the electrical double layer at
the interface mercury/dodecyl amine chloride (DAC)
by Aide TURUIZUMI solution was measured. Excess sodium chloride has
Adsorbents (3SZ4, 6SZ4) with varying pore-size distri- been added as a supporting electrolyte. The pH of the
butions are prepared by treating the sugar charcoal solution was about 6.0. At the concentration of 1 .5 X
(SZ4) with vinyl chloride polymer to different degrees, 10-5 N of DAC, two desorption peaks cleary appear .
the porous structure of the former has been determined These peaks which disappear by the addition of small
previously. The porous structures of these adsorbents quantities of HCI, probably are due to the desorption of
dodecyl amine molecules produced by the hydrolysis .
(3SZ4, 6SZ4) have been studied in the previous reports.
The characteristic behaviors in adsorption of n-mono- When the solution is buffered , peaks are not detected
carboxylic acid, benzene and n-heptane , " the sieving even under the saturated condition (pH 6 .8) . The
coefficient ", and the Dubinin's equation for the isotherm concentration dependence of the form of differential
of adsorption of vapors on active carbon are discus- capacity vs. voltage curve which is very complicated ,
sed. The following conclusions have been obtained . was discussed in comparison with the results previously
0) The pore-size distributions of the adsorbents ex- obtained.
amined (3SZ4, 6SZ4) are tri-disperse as SZ4 (ii) The Department of Physics and Chemistry, Gakushuin University; Toshima-
peaks in transitional-pore distribution, investigated with ku, Tokyo, Japan
the high-pressure mercury porosimetry method and the
isothermal benzene adsorption method , are calculated to
be appreciably different from each other . (iii) As the
pore space being filled up, their characteristic behaviors
in adsorption approached to that of the adsorbent 5
4. Nippon Kagaku 7asshi
(iv) Some cases in accord, and the others not in accord , Far Infrared Spectra of Gaseous Formic Acid
with the Dubinin's formulae . and Aceti
This diversity in the Acid
adsorption can be attributed to the magnitude of the
dimension of adsorbate molecule relative to the size of by Yasuo NAKAI and Kozo HIROTA*
the pore in adsorbent .
The far infrared absorption spectra of fo
rmic acid
Nagoya Municipal Industrial Research Institute; Atsuta-ku and acetic acid in the gaseous state were
, Nagoya, J observed in
apan
the region from 300 cm . -1 to 65 cm. -1 Associated dimer
 A64 Nippon Kagaku Zasshi Vol. 81 No. 6 (1O)

of formic acid and of acetic acid had bands near 240 dingly, it was- presumed that radon was not supplied
cm.-1 and 155 cm. -1, and near 177 cm.-', respectively. from the surface water shallower than 2 meters from
They are ascribed to the intermolecular vibrations the ground surface, but from the spring water contain-
between two monomers making up acid dimer by hydrogen ing chloride. Relations between the chloride content of
bonding. But it is noteworthy that their feature differs Matsubara Mineral Spring and water level of both the
markedli, e. g. in the cases of HCOOH, CH3COOH and River Misasa and the ground water were also described .
CD3COOH, each spectrum was double, while in the Balneological Institute, Okayama University; Misasa-cho, Tottori ,
cases of HCOOD and CH3COOD, each spectrum was Japan
single. The doublet splitting may be shown to arise
from the combination between intermolecular vibration
and energy level splitting resulting from a double
minimum in the potential energy curve for the proton.
Nippon Kagaku Zasshi, 81, 891^-895 (1960)
*Faculty of Science , Osaka University; Kita-ku, Osaka, Japan A Study on the Radioactive Decontamination The Ef-
fects of Condensed Phosphates on the Radioactive
Decontamination of Various Metal Surfaces

by Yuzo TAJIMA and Yoshiki WADACHI

In order to study the radioactive decontamination of

2. Inorganic Chemistry and Geochemistry
various metal surfaces such as iron, stainless steel,
copper, brass, lead and aluminum, they were first con-
taminated with "Co and with fission products. Using a
Nippon Kagaku Zasshi, 81, 884-•-891 (1960) standard test washing machine, these contaminated
Chemical Researches on the Hot Springs of Misasa, Tottori surfaces were rinsed with aqueous solutions of condensed
Prefecture, Japan phosphates. At the same time, the relationships between
by Takeshi SUGIHARA pH and complex forming abilities of the condensed phos-
phates were measured for CoC12 and fission products.
VII. On the Variation of the Amount of Spring Flow, The results obtained both for the decontamination and
Surface and Ground Water Levels at Misasa Hot Spring complex formation measurements indicated the suitable
Area (pp. 884-887) condition for decontamination of the metal surfaces by
the condensed phosphates. The suitable decontamination
The amount of spring flow, the water level of the
procedure is offered as follows: condensed phosphates;
River Misasa, and the ground water level at Misasa
0.1-4.01 mol./l., temperature; 30°C, acidity; pH
Hot Spring area, Tottori, were surveyed for one year
In this temperature, these condensed phosphates are
period starting in May, 1952. In general, the amount not suffered from decomposition, moreover, general metal
of spring flow had a tendency to increase during sum-
surfaces may be uncorrosive at this acidity.
mer. It was presumed that waters of both the ground
and the river had influence upon the flow rate Japan Atomic Energy Research Institute, Health Physics Divison;
and on the chloride content of the hot spring waters, Naka-gun, Ibaraki, Japan

but the ground water appeared to have larger influence

upon the hot spring waters than the river water did.
This report also describes the relations between (1) the
water level of the River Misasa and of a well in the
Nippon Kagaku Zasshi, 81, 896—.402 (1960)
area, (2) the flow rate of spring and its temperature,
Geochemical Studies on the Radioactive Sediments. 11^-111.
silicate, and radon content, (3) the river water level
and the contents of silicate and magnesium, and (4) the by Masanobu SAKANOUE
ground water level and magnesium content.
II. The Uranium Contents in the Natural Waters in the
Ningyo-Pass Mining Area (pp. 896-^-898)
VIII. On the Variation of Chemical Components of a
To confirm how much uranium is being leached from
Newly-found Spring in Misasa (pp. 887-891)
the sedimetary rocks and moving in the present natural
Chemical components of the mineral spring water of water, the uranium contents were determined on the
Matsubara newly-found in Misasa Hot Spring area, samples of underground waters inside the drift of the
Tottori, were determined continually from November, Ningyo-Pass Mine as well as the surface waters of the
1952 to April, 1953 and from November, 1955 to Novem- rivulets and the stream near the mine. The sample
ber, 1956. The res,ults showed that the maximum value waters were first filtered and acidified with nitric acid
of radon content amounted up to 1088 Ma ches (3960 x for storage. Uranidm was concentrated by the co-
10-10 curies per liter) which was the highest observed precipitation with aluminum phosphate and then analys-
so far in Misasa Hot Springs, and that positive correla- ed by the method of front paper-chromatography. The
tions in the chloride content were recognized between contents of uranium in the samples covered the range
this spring and six of 8 springs. Moreover, a negative from some micrograms to some hundred micrograms
correlation was recognized between the chloride content per litre. From these results, it is likely that uranium
in monthly average of the spring and the amount of is more reachable into the present natural waters from
rainfall in a month, but a positive correlation existed the unoxidized zone containing the uraniferous mineral
between the radon and the chloride contents. Accor- waters from the unoxidized zone containing the uram-
 Abstracts A 65

ferous mineral " ningyoite " than from the oxidized Nippon Kagaku Zasshi, 81, 906---912 (1960)
zone containing autunite. This fact was confirmed in Co-precipitation of Permanganate Ion with Lead Sulfate
the laboratory leaching tests in which the ores obtained
by Kenjiro HAYASHI and Yasumitsu UZUMASA
from both zones were leached with solutions of various
PH. When a mixed solution of sulfuric acid and a per-
manganate is added to lead nitrate solution, a part of
permanganate is co-precipitated with lead sulfate. The
III. Uranium, Phosphorus and Arsenic in the Sedimentary amount of permanganate co-precipitated is approximately
Ore Deposits Near Ningyo-Pass in Japan (pp. 898-^-902) proportional to the concentration of permanganate in
In order to throw a light on the origin of uranium the solution and is influenced by the amount of potas-
sium or sodium nitrate added. In the system of PbSO4-
ore deposits in the sandstone and conglomerate beds,
KMn04, the permanganate content in the precipitate
these geochemical studies were made on Ningyo-Pass
increases with either increasing concentration of potas-
Mine Japan. The uranium contents in many parts of
sium nitrate or decreasing concentration of sodium
those sedimentary beds were determined by the method
nitrate in the solution. In the system of PbSO4-NaMnO4,
of front paper-chromatography devised by the present
the permanganate content increases with increasing con-
author. The localities for the studies were the unoxi-
centration of potassium nitrate as well as sodium nitrate
dized zone where " ningyoite " was found, the oxidized
in the solution. However, the amount of permanganate
zone where autunite was seen, their coexisting zone, and
coprecipipitated with lead sulfate is not affected as long
some shale beds containing fairly high amounts of
uranium. The arsenic and phosphorus contents in the as the concentration of potassium or sodium nitrate
same sample were also determined by the improved remains lower than that of permanganate in the solution.
Gutzeit method and the molybdenum blue method re- Within a certain limit the relationship between the
spectively. As a result, it was found that the uranium amount of permanganate in the precipitate and the
and phosphorus contents in the unoxidized zone had a sodium or potassium content in the solution is given by
close interrelation and it is likely that uranium in these 4C=K[41lf]V", where41C is the increament or the decrea-
sediments was deposited mainly as the compound whose ment of the amount of permanganate in the precipitate
composition is corresponding to " ningyoite " , a and [AM] is the increament of the concentration of
new
uranous calcium phosphate mineral. Furthermore sodium or potassium ion in the solution. K and n are
, it
was supposed from the relations between the contents of constants. The amount of permanganate co-precipitated
uranium and arsenic that the existence of pyrite having decreases with increasing concentration of lead nitrate
the high arsenic content would have some connection in the mother liquor or increasing temperature of the
with the deposition of uranium. Moreover, the facts solution. There is no evidence that the permanganate
concerning the movement and concentration of uranium co-precipitates with lead sulfate in the form of Pb (Mn04)2 ,
,
phosphorus and arsenic in the oxidized zone were found. which is expected from the Paneth-Fajans-Hahn rules .
The permanganate in the precipitate is inert toward
Balneological Institute, Okayma University; Misasa-cho , Tottori, oxalate.
Japan
Faculty of Science, Hokkaido University; Sapporo-shi , Hokkaido, Japan

Nippon Kagaku Zasshi, 81, 903^-906 (1960)

Geochemical Investigations of Hot Springs in the Izu-Hakone
Nippon Kagaku Zasshi, 81, 912-915 (1960)
Province. III. The Geochemical Significance of Similarity
Chemical Investigations of Hot Springs. LVIII. On the
between Atami and Ito Balneological Activities Minor Constituents of Shikabe Spa

by Masayo MUROZUMI by Yasumitsu UZUMASA and Hideo AKAIWA

Balneological activities in the Izu-Hakone province Shikabe Spa in Hokkaido has several hot springs
that occupies the important area in the Fuji volcanic along the sea shore of the Pacific Ocean . It has been
zone have been found by the statistical treatment of already known that there is an inverse correlation between
geochemical data to have their origin in two kinds of Cl- and HCO3- contents of these springs . The minor
hydrothermal waters, one enriched with chloride ion and constituents (Cu, Pb, Zn and Mn) of each spring were
the other with sulfate ion . In Atami and ItO areas having determined and the manner of introduction of these
the largest activities in this province , the following
constituents to spring waters was discussed . It was
facts have been ascertained that each activity depends
observed that the contents of the minor constituents
on these both kinds of waters frotn the unknown origin
increase from north-west to south-west in the district
and forms many kinds of the secondary waters of the
and their changes are nearly parallel to the increasing
different chemical property by mixing in the different
tendency of HCO3- and SO42- . On the other hand , they
proportion. Observed results of geochemical character vary almost inversely with Cl- and temperature of these
of these secondary waters agree very well with statistical
hot springs. Our result suggests that Shikabe Spa might
ones.
be formed of two different types of water systems
Geological Survey of Japan; Kawasaki-shi , Kanagawa, Japan one is the water of high temperature containing much
and the other, the water of low temperature con -
taining carbonate and sulfate . The minor constituents
of this spa are considered to be derived from the latter
.
Faculty of Science, Hokkaido University; SaPPoro -shi, Hokkaido
, Japan
 A66 Nippon Kagaku Zasshi Vol. 81 No. 6 (19(30)

Nippon Kagaku Zasshi, 81, 920--,927 (1960)

3. Analytical Chemistry Studies on Inorganic Constituents in Biological Materials .
XIV. Thallium, Selenium and Arsenic Contents in Fishes
and Shells of Minamata District
Nippon Kagaku Zasshi, 81, 915-.418 (1960)
by Hiroshi HAMAGUCHI*, Naoichi OHTA, Naoki ONUMA* and
Rapid Analysis of Alkaline Earths. I. A New Separation
Katsuhiko KAWASAKI
Method of Strontium from Calcium by Use of Dihydroxy-
Since 1953 many fishermen of the Minamata district,
ethylglycine as a Masking Reagent
Kumamoto Prefecture, Kyushu, have been sufiering from
by Susumu TAKAMOTO a peculiar disease called " Minamata disease ". The
Dihydroxyethylglycine forms weak complexes with casuse of the disease is attributed to an intake of
marine animals of the district. Thallium, selenium and
alkaline earths in alkaline medium. Its strontium com-
arsenic contents in about 20 kinds of fishes and shells
plex has lower stability than calcium complex, hence if
caught at and near the Minamata Bay were determined.
ammonium sulfate is added to an ammoniacal solution
For comparison, three kinds of fishes gathered in Tokyo
containing strontium and calcium complexes, only stron-
were also analysed. No essential difference was found
tium sulfate precipitates by heating. Alcohol is also
added for completion of the precipitation. The solution between the two groups of samples. As for the distri-
is ice-cooled for one hour, then centrifuged. Washed pre- bution of each constituents in marine animals, the fol-
cipitate is dissolved with excess of disodium ethylene- lowing mean values were obtained (in p.p.m.) :
diaminetetraacete solution, and the strontium can be T1 0.34±0.12, Se 0.77±0.22, As 0.59±0.22 in viscera;
T1 0.08±0.02, Se 0.17±0.04, As 0.22±0.09 in meat;
determined by back-titration with magnesium solution
at pH 10 by the usual way. By the method, many T1 0.11±0.03, Se 0.20±0.07, As 0.23±0.07
in bone and shell.
samples containing less than 0.2 m mol. of strontium
and calcium in 2 ml. can be analysed much more rapidly These values are extremely high as compared with the
contents in sea water, the enrichment factor for the
than by ordinary extraction method. Less than 0.2
elements in marine organisms over sea water being 104
m mol. of magnesium and potassium, 1 m mol. of sodium,
for thallium and 102 for both selenium and arsenic.
3 m mol. of ammonium and 1 in mol. of anions such as
The contents of the three elements in the sediments
nitrate, perchlorate, chloride, bromide, iodide, thiocyanate
and acetate do not interfer. But most of the anions of the Minamata Bay and other marine environment were
which precipitate with calcium interfer. also determined.
*Tokyo Kyoiku University; Bunkyo-ku
Department of Physics and Chemistry, Gakushuin University; Toshima- , Tokyo, Japan

ku, Tokyo, Japan

Nippon Kagaku Zasshi, 81, 918-,420 (1960) Nippon Kagaku Zasshi, 81, 927-431 (1960)
Determination of Metallic Ions by Means of their Oxalates. Analyses of Natural Waters by Ions Exchanger

XI. On the Determination of Thorium in the presence of Separation of Metallic Ions with Formate Buffer Solution

Zirconium by Hiroyuki TSUBOTA

by Kyozo KAWAGAKI Ion exchange method for determining the constituents

It was already announced that certain conditions in natural waters has been studied. Using the column
should be required for the determination of Th by the of cation exchange resin (cb 1.1 x 10 cm.), the major con-
oxalate method. In the present paper, the oxalate stituents in waters were easily and completely separated.
method for the determination of Th in the presence of Alkali metals wers first eluted with dilute hydrochloric
acid or a mixed solution of 1 M formic acid and 1 M
Zr was studied. The reaction between Zr salts and
ammonium formate. Thereafter, iron, aluminum, manga-
oxalic acid is so complicated that it has not yet been
nese, magnesium, calcium, and strontium were separately
studied from the point of analytical chemistry. The
eluted with the mixed solutions of formic acid and
object of this investigation is first to find the conditions
ammonium formate. In these cases, the ions separated
under which Zr is to be precipitated as oxalate and to
in the effluents could be easily determined by titrimetric,
establish a method for determination of Th by using
colorimetric, and flamephotometric methods. This
oxalic acid alone in the presence of Zr. The results
method of separation can also be used in determining
showed that Th can be determined quantitatively in the
minor constituents as well as radioactive nuclides in
presence of Zr when the following conditions are satisfied.
waters, and is available to the analyses of minerals and
1) The molar ratio of Zr to Th is 0.9 or less. 2) The
ceramic materials.
amount of oxalic acid is 20 cc when 0.5 N solution is
used. 3) The total volume of the solution is 100-200 National Institute of Radiological Science; Chiba-shi, Chiba, Japan
cc. 4) The time of heating on a water bath is 30 min.,
and that of standing is one hour.
Faculty of Engineering, Niigata University;- Nagaoka-shi, Niigata,
Japan
 AbstractsA 67

hydantoin, the dehydrating condensation took place bet-

4. Organic Chemistry and Biological Chemistry ween carboxyl group of the aldehydic acid and NH
group at the 1-position of hydantoin, formig isocarbostyril-
2,3-dicarbonimid as an intermediate product, whose hy-

Nippon Kagaku Zasshi, 81, 931---933 (1960) dantoin ring was then cleaved by hydrolysis and decar-
boxylation. The similar reactions were observed in the
Reaction of a-Pinene with Formaldehyde
cases of the condensation of o-phthalaldehydic acid with
by Yuichi WATANABE 3-phenylhydantoin and 3-methylhydantoin whose 3-posi-
tion of hydantoin was occupied by an aryl or an alkyl
Under the following conditions, the condensation reac-
tion of formaldehyde with a-pinene has been studied: 1) group.
in acetic acid with phosphoric acid as catalyst, 2) thermal
condensation, 3) reaction with formalin (37% HCHO aq.
sol.) in the presenece of HC104. Under the condition IV. On the Condensation Reaction of o-Phthalaldehydic
1), 6-hydroxymethy1-1,8(9)-p-menthadiene was obtained, Acid with Thiohydantoin and Glycocyamidine (pp. 940-----942)
and in the case of 2), 3-hydroxymethy1-2(10)-pinene was
Condensation of o-phthalaldehydic acid with thiohydan-
obtained, while under the condition 3), 1,3-dioxane
toin resulted in the dehydrating condensation between
derivatives were obtained.
aldehyde group and methylene group. Along with it,
Saisei Camphor Co., Ltd.; Fukiai-ku, Kobe, Japan the dehydrating condensation took place between NH
group at the 1-position of thiohydantoin and carboxyl
group of the aldehydic acid. In this case, however-
hydantoin ring of the condensation product was rather
stable, being different from the reaction of hydantoin
Nippon Kagaku Zasshi, 81, 934"--938 (1960) and o-phthalaldehydic acid. The similar reaction was
Synthesis of Glutaric Acid Derivatives from Cyclopentadiene. observed in the case of the condensation of o-phthalalde-
IV. The Synthesis of a-Hydroxyglutaric Amide and its hydic acid with glycocyamidine. In other words, the
Cyclization by Heating hydantoin ring of the condensation product is rather
stable in 2-substituted hydantoin derivatives. In this
by Yoshio KAWAI
reaction, one molecule of o-phthaladehydic was also
By the reaction of the mixture(I) which consists of condensed with NH at the 2-position of glycocyamidine
the ester of r-butyrolactone-r-carboxylic acid and of a- with the cleavage of hydantoin ring.
hydroxyglutaric acid with ammonia, a-hydroxyglutaric
amide(II) was obtained almost quantitatively. The con-
dition of cyclization of II by heating was studied. When V. On the Condensation Reaction of o-Phthalaldehydic
II was heated at about 200°C under atmospheric or
Acid with 1-Methylhydantoin (pp. 942----943)
reduced pressure, r-butyrolactone-r-carboxylic amide
was obtained as a main product. On the contrary, Condensation of o-phthalaldehydic acid with 1-methyl-
when II was heated at above 200°C in an autoclave in hydantoin in the presence of anhydrous sodium acetate,
the presence of liquid ammonia or water, the amide glacial acetic acid and a small amount of acetic anhydride
(III) or ammonium salt(IV) of 2-pyrrolidone-5-carboxylic gave 1-methyl-5-phthalidyl-hydantoin and 3-acetoxy-
acid were severally obtained as main product. Ac- phthalid. In this case, the formation of isocarbostyril
cordingly, by using the ammonolysis of I and the de- ring was not observed, becasuse 1-position of hydantoin
hydrating cyclization of II in the presence of water, it was occupied by methyl group.
was found that glutamic acid was obtained in above
80% yield of the theoretical.

Sanko Co., Ltd.; Kawasaki-shi, Kanagawa, Japan VI. On the Condensation Reaction of o-Phthaladehydic
Acid with Creatinine (pp. 943-^-944)

Condensation of o-phthalaldehydic acid with creatinine

gave two condensation products. One of them was the
condensation product of one molecule of creatinine with
Nippon Kagaku Zasshi, 81, 938—.444 (1960) one molecule of o-phthalaidehydic acid , and the other,
Condensation Reactions of o-Phthalaldehydic Acid . 111"--VI. consisting of one molecule of creatinine with two mole -
cules of o-phthalaldehydic acid.
by Sum i NAGASE
The Medical Institute of Sasaki Foundation; Chiyoda -ku, Tokyo , J
III. On the Condensation Reaction of o-Phthalaldehydic apan
Acid with Hydantoin , 3-Phenylhydantoin and 3-Methyl-
hydantoin (pp. 938^-940)

Condensation of o-phthalaldehydic acid with hydantoin

in the presence of anhydrous sodium acetate
, glacial
acetic acid and a small amount of acetic anhydride gave
two condensation products. In this reaction , along with
the dehydrating condensation between aldehyde group
of o-phthalaldehydic acid and methylene group of
 A68 Nippon Kagaku Zasshi Vol. 81 No. 6 (1960)

Nippon Kagaku Zasshi, 81, 944--950 (1960) with smaller amounts of the sample. p-Chloranilides are
Studies on Hydroxycarboxylic Acids. white crystals with moderate high melting points
, and
are suitable for identifying the fatty acids . Melting
by Takeyoshi HAGA
points of the mixtures of two p-chloranilides were
IV„ Condensation of Aromatic Alcohols with Lactic Acid measured, and curves were drawn. This method was

(pp. 944,--946) found to be suitable for the analysis of fatty acid

mixtures.
p-Methoxybenzyl alcohol (I), o-methoxybenzyl alcohol
Department of Applied Chemistry, Faculty of Science and Engineering
(II) and phthalide (III) was condensed with lactic acid , Ki
nki University; Fuse-shi, Osaka, Japan
as a test of the new reaction reported in Part III of this
series (Nippon Kagaku Zasshi, 81, 277 (1960)) . From I
a-hydroxy-r-p-methoxyphenylbutyric acid was obtained
very easily, II and III gave a-hydroxy-r-o-methoxyphenyl-
butyric acid and a-hydroxy-r-o-carboxyphenyl-butyric acid
(IV) respectively. The compound IV is very soluble in Nippon Kagaku Zasshi, 81, 954"-959 (1960)
water, but its ferric salt is insoluble.
The Sequence of Formation of Oil in Castor Seed . VII,
Studies on the Biosynthesis and Fragmentation of "C.
V. The Action of Heat on Aromatic a-Hydroxycarboxylic labeled Ricinoleic Acid in Castor Seed Oil
Acids (pp. 946---948) by Kazuyuki MIHARA

Aromatic aldehydes were obtained by heating some When the aqueous solution of D-glucose-1-14C was
aromatic a-hydroxycarboxylic acids at 250---300°C. a- absorbed into the stems of the growing " Ricinus Corn-
Hydroxyl-phenyl-butyric acid decomposed at 250°C into munis, Linn " plant: (A) On examining labeled posi-
hydrocinnamaldehyde, carbonmonoxide and water. In tions of "C on C-1, 2, 3, 4, 12 and 13 positions in the "C-
the same way a-hydroxy-r-p-methoxyphenylbutyric acid ricinoleic acid molecule, it was found that "C atoms
gave p- methoxyhydrocinnamaldehyde; a - hydroxy fi - were at C-2, 4 and 12-positions. From this fact it was
methyl - r - phenylbutyric acid gave a-methylhydrocin- confirmed that conversion of D-glucose to ricinoleic acid
namaldehyde; and a-hydroxy-p-benzyl-r-phenylbutyric
in the "Ricinus Communis, Linn." plant might take place
acid gave a-benzylhydrocinnamaldehyde. From these with C-C units. (B) Isolating ricinoleic acid, saturated
aldehydes the corresponding 2,4-dinitrophenylhydrazones fatty acids and unsaturated fatty acids from the "C-
were obtained.
castor seed oil and examining differences in their radio-
activities, it was found that the order of their activities
was as follows: unsat. fatty acids)-ricinoleic acid> sat.
VI. Condensation of Aliphatic Alcohols with Lactic Acid
fatty acids.
(pp. 948,950)
Musashi Institute of Technology; Setagaya-ku, Tokyo, Japan
The new reaction previously reported (Nippon Kagaku
Zasshi, 81, 272 (1960) .) was successfully applied to the
condensation of aliphatic alcohols with lactic acid. n-
Amyl, n-hexyl and n-octyl alcohols gave a-hydroxy-
caprylic, a-hydroxypelargonic- and a-hydroxyundecanoic
acids respectively. These aliphatic hydroxycarboxylic Nippon Kagaku Zasshi, 81, 959-962 (1960)
acids decomposed thermally at 250—,300°C into aldehydes,
Studies on a-Methylenepolymethylene Diisocyanates
carbon monoxide and water.
by Masao SATO
Central Research Laboratory, Mitsubishi Chemical Industries Limited;
Kawasaki-shi, Kanagawa, Japan
a-Methylenetetramethylene diisocyanate
CH,
and a-methyleneoctamethylene di-
OCN- C -(CH,) 3-NC(
CH,
isocyanate were synthesized from
OCN-C- (CH9 ) 7-NCO
Nippon Kagaku Zasshi, 81, 950"-953 (1960) the corresponding acids via acid chlorides and their
On p-Chloranilides of Saturated Fatty Acids and Oleic azides. By the reaction between each of these isocyan -
Acid ates and amine or alcohol, the normal addition product,
the corresponding substituted urea or carbamate, was
by Hiromu KAMEOKA
produced. These derivatives were confirmed to show
Amides and anlides of many fatty acides are well the similar behavior to that of N-1-alkenyl-urea and
known, but p-chloranilides of only four acids including N-1-alkenylcarbamate
acetic acid has been described in the literature. The Tokyo Institute of Technology, Research Laboratory of Resources
author synthesised p-chloranilides of fourteen saturated Utilization; Meguro-ku, Tokyo, Japan
acids and oleic acid. They were readily prepared with
good yield by one of the two following methods: (a) by
the action of acid chlorides on p-chloraniline. (b) by
boiling the equivalent mixture of free acids and p-chlor-
aniline in p-cymene solution. The second method was
more convenient, and p-chloranilides may be synthesised
 Nippon Kagaku Zasshi, 81, -962^-969 (1960) complex were different from other well-known macrolides,

Condensation Reactions of Aminoalcohols with Imides. III. erythromycin, magnamycin, and spiramycin.

Condensation Products of N-Alkyl-N-arylaminoethanols *Research Institute, Toyo Jozo Co., Ltd.; Ohito-machi, Shizuoka, Japan

with Succinimide or Phthalimide

by Kazuo NAKAJIMA

In the present paper, it was shown that N-alkyl-N-

aryl-amino. ethanols condensed, like N, N-dialkylamino-
ethanols described in the previous paper, with succinimide Nippon Kagaku Zasshi, 81, 971''973 (1960)
or phthalimide under elimination of water to form ,a new
The Addition Reaction of Nitrogen Trioxide to Methyl
N-C linkage, and these condensation products could be Crotonate
easily hydrolysed into the corresponding N-alkyl-N-
arylethylenediamine derivatives. These processes may by Kazuo YAMAGISHI and Yoshie ISHIBIKI
be represented by the following schemes;
0C —HO
Addition of nitrogen trioxide to methyl crotonate has
Ar(R)NCH2CH2OHHN<>R' been studied in oder to define the course of addition of
( ) OC nitrogen trioxide to asymmetrically disubstituted olefins.
OC21120 When the reaction was carried • out in ether at 0°C,
Ar(R)NCH2C112N<>R'
> methyl-a-nitrocrotonate and rnethyl-a-hydroxy-/9-nitro
OC
butyrate were obtained in 47% and 23% yields respectively.
COOH
Ar(R)NCH2CH2N}1.2
IV‹ The products were identified by converting them to
(II) COOH corresponding amino acids. It was concluded that the
CO affixation of nitro group to methyl crotonate had no
(Ar—
aryl, alkylandl?'‹CO >NH—
imide
of selective rule giving the mixture of a-nitro and p-nitro
derivatives nealy in the same proportion. The r( s
dicarboxylic acids). may be explained by assuming both ionic and radical
Ar and R radicals of the N-alkyl-N-arylaminoethanols intermediates involved in this reaction.
(I) and the N7alkyl-Marylethylenediamines (II), now
prepared, have been tabulated below. La4aratory, of Organic 'Chemistry, Tokyo Institute of Technology;
Meguro-ku, Tokyo, Japan
Ar R Ar
C6H5- CH3- C
61-15- /—\ C
6H5- C2H5-
C6H5- n-C3H7- CI-C> CH3-
C6H5- i-C3H7- OCH
C 3
6H5- CH2CHCH2-CH3- Nippon Kagaku Zasshi, 81, 974---976 (1960)
5-
C6H11- n-C49<-=> Studies on the Derivatives of Propargylalcohol. V.
C6H5- i-C4119- H5C20-<I> CH3- Synthesis of Pyrazole Compounds by the Reaction of
C6H5- i-051411- CH
3 Diazomethane with Propargylamine or Propargylmercaptan
C6H5- <=._)-CH2- (0,m,p) CH- Derivatives
Kyoto Works, Teikoku Chemical Industry Co., Ltd; Nakagyo-ku,
Kyoto, Japan by KAurrasa SATO and Hiroshi INOUE

The addition reaction of the derivatives of propargyl-

alcohol with diazomethane was investigated. Propargyl-
amine reacted with diazomethane in ether and afforded
an arninomethylpyrazole. This compound was identical
with 3-aminomethylpyrazole. Similarly 3-N-acylamino-
Nippon Kagaku Zasshi, 81, 969—.471 (1960)
methylpyrazole, N - benzoylaminomethylprazole and
Studies on Leucomycin. I. Paper Chromatographic Analysis
phthalimidomethylpyrazole were prepared from N-acyl-
of Leucomycin and Other Macrolides
propargylamine. With propargylmercaptan and pro-
by Jinnosuke ABE*, Yasuo SUZUKI*, Tetsuo WATANABE* anc pargylthioether similar experiments were attempted.
Kazuo SATAKE Only p-nitrophenylpropargylthioether gave the correspon-
ding 3-substituted pyrazole. This compound was de-
Leucosnycin, a basic antibiotic produced by Streptomyces
rived to a new heterocyclic sulfone compound, 3- (p-
kitasatoensis Hata, was proved by paper chromatographic
aminophenylsulfurylmethyl) -pyrazole.
analysis, to be a mixture composed of at least six
biologically active components, Al, A2, BI, B2 , B3 and Department of Technology, Yokohama National University; Minami-
B4. Discrimination between A and B groups could be ku, Yokohama, Japan
easily made from their Rf values on the chromatogram
developed with n-butyl acetate containing 1/15 mol .g.
sodium phosphate buffer (pH 5.9) ; while that between
Al and A2 or among Bl, B2, B3 and B4, from the Rf
values obtained with 1/15 moll/. sodium phosphate buffer
(pH 8.0) containing n-butyl acetate on a liquid paraffin..
treated filter paper. In addition, these results indicated
that all six antibiotics contained in the leucomycin
 A 70 Nippon Kagaku Zasshi Vol. 81 No. 6 (1960)

Nippon Kagaku Zasshi, 81, 976—.479 (1960) reducing the acids (IVa) and (IVb) above-stated with
Study on the Structure of Vinyl Polymers with Some Model sodium amalgam.
Compounds Chemical Laboratory, Faculty of Education, Shinshu University
;N
agano-shi, Nagano, Japan
by Masaru SHIRAKI and Eiichi NAGAI

The structures of polyvinylalcohol, polyvinylhalides,

and polyvinylacetate were studied with the aid of a low
molecular weight model substances by comparing the
infrared spectra. As a general, it is necessary to pre- Nippon Kagaku Zasshi, 81, 981-984 -

pare two models which correspond to the jsiort-range Phenols in the Essential Oil of Thujopsis Dolabrata Sieb .
sequences in the polymer chain, that is, the ones which et Zucc.
have isotactic and syndiotactic configurations, respec-
by Akira YOSHIKOSHI
tively. The meso- and racemic-2,4-disubstituted pen-
tanes were given as the two simplest models. Pentane- No phenol other than carvacrol have been isolated in
2,4-diol was prepared by hydrogenation of acetyl-acetone the essential oil of Thujopsis dolabrata. The present
using the Raney nickel catalyst, and the separation paper reports the presence of m-isopropyl phenol (22%),
into a and 9 form isomers was succeeded by ion ex- 4-isopropylsalicylaldehyde (7%) and a small amount of
change chromatography. The stereoisomers of 2, 4- o-isopropylphenol and p-cresol, accompanied by carva-
dihalogenopentane and 2, 4-diacetoxypentane were pre- crol which is the main constituent (65%) . Both p-
pared by halogenation and acetylation of the a and p isopropyltropolone (r-thujaplicin) and p-isopropyl phenol
diol isomers using the hydrogen halides and acetic are absent, while the presence of o- and m-isopropyl
anhydride reagents, respectively. The observed physical tropolone (a- and p- thujaplicin) have been well known
properties of a form isomers, that is, strong adsorption in the literature.
to ion exchange resin, low melting point and I. R.
Ogawa & Co., Ltd.; Chuo-ku, Tokyo, Japan
spectra showed that the a form was probably meso-form.
It was also known that I. R. spectra of these isomers
were quite similar to these of the corresponding poly-
mers, and that these models could afford the useful
way for clarifying the molecular structure of the vinyl-
polymers. Note

Osaka Industrial Research Institute; Oyodo-ku, Osaka, Japan

Nippon Kagaku Zasshi, 81, 984--485 (1960)

Separation of a Micro Amount of Inorganic Phosphate in
Urine by Paperchromatography.
Nippon Kagaku Zasshi, 81,979-..981 (1960)
by Tadakatsu IWANAGA
Syntheses of Two Amino Acids with Rhodanine
Chloride and sulphate are the interfering ions in the
by Chiaki TSUCHIYA
colorimetric determination of inorganic phosphate. Here,
Syntheses of D, L-,3-(2-thieny1)-alanine and D, L-3-methoxy- the separation of inorganic phospate from chloride, sul-
4-hydroxyphenylalanine with rhodanine has been de- phate, arsente ions and the various organic phosphates
scribed. These new a-amino acids were synthesized by in human urine was studied by means of the paper
the following processes from 2-thienylidene-rhodanine(lla) chromatography. The inorganic phosphate was separated
and vanillidene-rhodanine(IIb) respectively. These by using methanol-formic acid-water (80 : 15 : 5) mixture
rhodanines, (Ha) and (IIb) , were obtained by condens- as solvent at room temperature. The strip (Toyoroshi
ing a-thiophenaldehyde and vanilline with rhodanine No. 51A) was developed for 25 cm. and the Rf value of
by Perkin reaction respectively and were transformed the phosphate was about 0.7. The strip was dried and
to /3-(2-thieny1)-a-thiopropionic acid (IIIa) and 3-methoxy- the part of the phosphate was cut off and was incinerated.
4-hydroxyphenyl-a-thiopropionic acid (Mb) by the reaction Then, colorimetric determination was carried out. This
with sodium hydroxide respectively. These acids, (Ma) method is suitable for the separation of true inorganic
and (Mb), were converted to 9- (2-thieny1)-a-oximino- phosphaste salt of human urine, and can be successfully
propionic acid (IVa) and 3-methoxy-4-hydroxyphenyl-a- separated. By this procedure, 0.2-4 pg. of P205 in 0.0025
oximinopropionic acid(IVb) by the reaction with hydroxyl- cc. of urine can be determined.
amine respectively. D, L-13-(2-Thienyl) -alanine and DO,- Faculty of Engineering, Gifu University; Naka-machi, Inaba-gun,
3-methoxy-4-hydroxyphenylalanine were obtained by Gifu, Japan