bluuebunny/crossref_metadata_2025 huggingface dataset:
THE HIGHLY UNSATURATED ACIDS IN SARDINE OIL. III. THE ISOLATION AND CONSTITUTION OF MOROCTIC ACID C8H28O2
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

Moroctic acid C18H28O2 has been isolated from a large quantity of Japanese sardine oil. For the determination of its constitution, methyl moroctate was subjected to ozonolysis. Among the products of ozonolysis, propionic acid, propyl aldehyde, succinic acid, succinic semi-aldehyde, methyl hydrogen succinate, methyl ester of succinic semi-aldehyde, carbon dioxide, acetic acid and acetaldehyde were found. Three last named compounds are considered to be formed by the secondary decomposition of malonic acid and the corresponding aldehyde which are derived from the =CH·CH2·CH= group. The presence of malonic acid, though in a small quantity, in the products of ozonolysis was also indicated. In the next place, tetrathiocyano-derivative was prepared from methyl moroctate, and it was subjected to ozonolysis. Among the products of ozonolysis, propionic acid, propyl aldehyde, carbon dioxide, acetic acid, acetaldehyde and an oily thiocyano-compound were recognised. The oily thiocyano-compound yielded, on elimination of thiocyanogen followed by hydrolysis, a decadiene-dicarboxylic acid (Δ3:4, 7:8-decadiene-1,10-dicarboxylic acid). Hence, the constitution of moroctic acid is established as Δ4:5, 8:9, 12:13, 15:16-octadecatetraenoic acid which is expressed by the following formula. CH_3·CH_2·CH=CH·CH_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·COOH
THE HIGHLY UNSATURATED ACIDS IN SARDINE OIL. IV. THE SEPARATION OF HIGHLY UNSATURATED C20-ACIDS
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

Highly unsaturated C20-acids have been separated from sardine oil and they were further separated into the portions of different degrees of unsaturation with the results that an eicosatetraenoic acid C20H32O2 was isolated and also the presence of an eicosapentenoic acid C20H30O2 was proved by separating a fraction, in which this acid is concentrated.
THE HIGHLY UNSATURATED ACIDS IN SARDINE OIL. V. THE CONSTITUTION OF EICOSATETRAENOIC ACID C20H32O2
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

The eicosatetraenoic acid separated from sardine oil was converted into the amyl ester, and the latter was subjected to ozonolysis. Among the products of ozonolysis were found: butyric acid, butyric aldehyde, succinic acid and amyl hydrogen succinate. The presence of succinic semi-aldehyde, succinic aldehyde and amyl ester of succinic semi-aldehyde was also indicated. Accordingly the constitution of the eicosatetraenoic acid is shown to be Δ4:5, 8:9, 12:13, 16:17-eicosatetraenoic acid as expressed by the following formula: CH_3·(CH_2)_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·COOH.
THE HIGHLY UNSATURATED ACIDS IN SARDINE OIL. VI.THE CONSTITUTION OF EICOSAPENTENOIC ACIDS C20H30O2
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

A concentrated fraction of eicosapentenoic acid containing an appreciable amount of eicosatetraenoic acid was converted into amyl ester and the latter was subjected to ozonolysis. Among the products of ozonolysis were found: succinic acid, amyl hydrogen succinate, amyl ester of succinic semi-aldehyde, carbon dioxide, acetic acid, acetaldehyde and a higher aldehyde (probably butyric aldehyde). The yield of these compounds and also the constitution of eicosatetraenoic acid (Δ4:5, 8:9, 12:13, 16:17) being taken into consideration, it was concluded that the eicosapentenoic acid had the following groups: =CH·CH2·CH=, =CH·(CH2)2·CH= and =CH·(CH2)2·COOH, of which it contained more than one of the group =CH·CH2·CH=. As the group at the CH3-side was left undetermined in these experiments, the constitution of the eicosapentenoic acid was not established with certainty. If, however, it is assumed that there are ethylenic linkings in 4:5-, 8:9- and 12:13-positions like in the eicosatetraenoic acid, the constitution must be Δ4:5, 8:9, 12:13, 15:6, 18:19-eicosapentenoic acid as expressed by the following formula: CH_3·CH=CH·CH_2·CH=CH·CH_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·CH=CH·(CH_2)_2·COOH.
ELECTROLYTIC OXIDATION OF ANILINE OIL
Authors: Yasui Toyokichi
Published: July 2006

(1) By the electrolytic oxidation of aniline oil in acid solution neither safranine nor fuchsine is produced.

(2) p-Aminodiphenylamine is first produced, it passes into emeraldine and finally into aniline black.

(3) p-Aminodiphenylamine reacts with aniline and homologues producing aposafranine.
A NEW GRAVIMETRIC METHOD FOR THE DETERMINATION OF LEAD AS LEAD SALICYLALDOXIME AND ITS SOLUBILITY MEASUREMENT BY USING ThB AS RADIOACTIVE INDICATOR
Authors: Ishibashi Masayoshi , Kishi Haruo
Published: July 2006

(1) Lead is quantitatively precipitated as salicylaldoxime compound from a neutral and a strongly ammoniacal solution of pH (Remark: Graphics omitted.) 6.5.

(2) The composition of the material precipitated and dried at about 105°C. is possibly Pb(C7H5O2N).

(3) The solubility of lead salicylaldoxime in pure water at 25°C, measured by the use of radioactive isotope Th B as indicator, is 1.37×103 per liter, i.e., 4.0×106 mol/l.
INFLUENCE OF CALCIUM ON CARBOHYDRATE METABOLISM
Authors: Harada Taichi
Published: July 2006

(1) The glucose tolerance on albino-rabbits was studied.

(2) The influence of calcium upon the activity of adrenalin on the blood sugar in the rabbit was experimented. It gave little change.

(3) An interesting relation between calcium and the carbohydrate metabolism of the body was observed: that is, calcium prevents considerably the elevation in both hyperglycemia and glycosuria which would occur when glucose alone or glucose-adrenalin without calcium was administered.
THE HIGHLY UNSATURATED ACIDS IN SARDINE OIL. IX. THE CONSTITUTION OF DOCOSAHEXENOIC ACID C22H32O2
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

1.A concentrated fraction of docosahexenoic acid was converted into the amyl ester, and the latter was subjected to ozonolysis. Among the products of ozonolysis were found: acetaldehyde, acetic acid, carbon dioxide, succinic acid and amyl hydrogen succinate. The presence of the aldehydes corresponding to succinic acid and amyl hydrogen succinate was also indicated. Of these compounds, carbon dioxide together with acetaldehyde and acetic acid is attributable to the secondary decomposition of the products derived from the group =CH·CH2·CH=. The yield of carbon dioxide indicated the presence of at least three of the group =CH·CH2·CH= in amyl docosahexenoate. Consequently docosahexenoic acid has the following groups: =CH·CH2·CH=, =CH·(CH2)2·CH=, and =CH·(CH2)2·COOH, of which it has at least three of the group =CH·CH2·CH=. The yield of C4-compounds (succinic acid and the corresponding aldehyde) obtained by the ozonolysis gave an indication of the presence of more than one of the group =CH·(CH2)2·CH= in docosahexenoic acid.

2. Although the group attached to the CH3-side and the respective positions of the groups CH·CH2·CH= and =CH·(CH2)2·CH= were left undetermined in these experiments, the most probable structure of docosahexenoic acid was derived from the results obtained above.
THE HIGHLY UNSATURATED ACIDS IN SARDINE OIL. XL THE CONSTITUTION OF NISINIC ACID C24H36O2 IN SARDINE OIL
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

Nisinic acid C24H36O2 has been separated from sardine oil, and its amyl ester subjected to ozonolysis. Among the products of ozonolysis were found: propyl aldehyde, propionic acid, asetaldehyde, acetic acid, carbon dioxide, succinic acid and amyl hydrogen succinate. Of these compounds propyl aldehyde and propionic acid are derived from the group CH3·CH2·CH=, whilst acetaldehyde and acetic acid together with carbon dioxide are attributable to the secondary decomposition of malonic acid and the corresponding aldehyde which are derived from the group =CH·CH2·CH=. The yield of carbon dioxide indicated the presence of more than two of the group =CH·CH2·CH=. Succinic acid and amyl hydrogen succinate are derived from the groups =CH·(CH2)2·CH= and =CH·(CH2)2·COOC5H11 respectively. Accordingly, nisinic acid was found to be composed of the following groups: CH3·CH2·CH=, CH·CH2·CH=(three), =CH·(CH2)2·CH= (two), and =CH·(CH2)2·CH= were not determined in these experiments. If, however, it is assumed that three of the ethylenic linkings in nisinac acid lie at 4:5-, 8:9- and 12:13-positions as is the case with previously studied moroctic, eicosatetraenoic and clutanodonic acids,the constipution of nisinic acid is expressed by the following formula:

CH3·CH2·CH=CH·CH2·CH=CH·CH2·CH=CH·CH2·CH=CH·(CH2)2·CH=CH·(CH2)2·CH=CH·(CH2)2·COOH
TETRADECENOIC AND DODECENOIC ACIDS IN SPERM OIL. I. TETRADECENOIC AND DODECENOIC ACIDS IN SPERM BLUBBER OIL
Authors: Toyama Yoshiyuki , Tsuchiya Tomotaro
Published: July 2006

Tetradecenoic acid C14H26O2 and dodecenoic acid C12H22O2 have been separated from sperm blubber oil. They are converted into dihydroxymyristic acid C14H28O4 and dihydroxylauric acid C12H24O4 respectively, and the methyl esters of these hydroxy-derivatives are subjected to the permanganate oxidation in acetone. From the results of an examination of the oxidation products, the following constitutions have been established:

Tetradecenoic acid CH3·(CH2)7·CH=CH·(CH2)3·COOH,

Dodecenoic acid CH3·(CH2)5·CH=CH·(CH2)3·COOH.

It is thus seen that tetradecenoic acid in sperm blubber oil is identical with physeteric acid (Δ5:6-tetradecenoic acid) in sperm head oil, whilst dodecenoic acid in sperm blubber oil, to which the name denticetic acid is assigned, is Δ5:6-acid and is an isomer of linderic acid (Δ4:5-dodecenoic acid) in the seed oil of Lindera obtusiloba.
ON THE OCCURRENCE OF NEW HIGHLY UNSATURATED FATTY ACIDS, C26H40O2 AND C26H42O2, IN TUNNY OIL
Authors: Ueno Sei-ichi , Yonese Chizuo
Published: July 2006

The mixed liquid acids obtained from the sample oil by cooling were converted into methyl esters which were fractionally distilled under a diminished pressure of 4 mm. From the highest boiling fraction, the authors separated a new highly unsaturated acid C26H40O2((Remark: Graphics omitted.)6) and also detected the occurrence of another new acid C26H42O2 ((Remark: Graphics omitted.)5) besides scoliodonic acid (C24H33O), nisinic acid (C24H36O2) and clupanodonic acid (C22H34O2). The present authors propose the names “thynnic acid” for the acid C26H40O2 and “shibic acid” for the acid C26H42O2.
STUDIES OF MONOMOLECULAR FILMS BY THE RIPPLE METHOD. II
Authors: Sasaki Tsunetaka , Sameshima Jitsusaburo
Published: July 2006

(1) The change of height of the capillary wave by the oil film has been measured, “the constant oil quantity method” being used. The substances tested are oleic acid, palmitic acid, myristic acid, tetradecyl alcohol, palmitonitrile, lauric acid, tripalmitin, triolein, ricinoleic acid, and ethyl palmitate.

(2) It has been found that there occurs some hysteresis phenomena in the subsiding action of the capillary wave by compression and expansion of the film.

(3) The areas per molecule of oils have been calculated from the kink point in the expansion curve of the film.

(4) Experiments have been done on mastic, the molecular weight of which being estimated at about 3600.
STUDIES ON THE RAMAN EFFECT OF ORGANIC SUBSTANCES. VI. RAMAN EFFECT OF SESQUICHAMENE AND SOME OTHER TERPENES
Authors: Matsuno Kichimatsu , Han Kwan
Published: July 2006

(1) The Raman spectra of the following substances have been measured: Sesquichamene. d-sabinene, d-α-pinene, d-verbenol, d,l-Δ1-terpinenol-(4), menthyl acetate, and isobornyl acetate.

(2) The occurrence of the intense line at Δν 1682cm.−1 seems to suggest that sesquichamene may have a linkage of 1-methyl-cyclohexene-(1) if cedrene has a linkage of 1-methyl-cyclopentene-(1).
STUDIES ON THE CONSTITUTION OF SHONANIC ACID, ONE OF THE TWO CHARACTERISTIC VOLATILE ACIDS FROM THE WOOD OF LIBOCEDRUS FORMOSANA, FLORIN. I. THE ISOLATION OF SHONANIC ACID AND ITS GENERAL PROPERTIES
Authors: Ichikawa Nobutoshi
Published: July 2006

(1) The existence of an unknown acid in the volatile part from the wood of Libocedrus formosana, Florin, or “Shônan-Boku” is reported.

(2) Shonanic acid is an unsaturated monobasic acid with a monocyclic structure of the formula C10H14O2, melting at 40–41°. Its amide melts at 116-117° and the anilide at 111-112°.

(3) Shonanic acid can be converted into tetrahydroshonanic acid by absorption of four atoms of hydrogen when reduced catalytically, while it absorbs only two atoms of bromine, and when reduced with sodium and ethyl alcohol an unsaturated acid, viz. dihydroshonanic acid (C10H16O2), is obtained. These experimental facts together with the fact that the molecular refraction of shonanic acid exhibits an eminent exaltation lead to the conclusion that conjugated double bonds exist in its molecule.

(4) Though tetrahydroshonanic amide melts at 144°, it was proved that the acid is quite different from dihydro-a-campholenic acid (C10H18O2, amide m.p. 144°).

(5) Shonanic acid isomerizes to isoshonanic acid by the action of hot strong alkali solution. Iso-acid melts at 45° and gives an amide melting at 107–108°.

(6) The isomerisation of shonanic acid to isoshonanic acid is accompanied by the elevation of the boiling point to the extent of 13°C. This phenomenon may probably be due to the migration of semicyclic double bond into the ring system of the acid, which must be ascertained by further investigations.
Studies on the Flow of Gaseous Mixtures through Capillaries. III. The Flow of Gaseous Mixtures at Medium Pressures
Authors: Adzumi Hiroshi
Published: July 2006

(1) The quantities of seven following simple gases and six gaseous mixtures flowing through the capillary have been measured at the pressures between 4 and 0.01mm.

&H_2,C_2H_2,C_3H_6,H_2∼C_3H_6;

&C_6H_6,CCl_4,CHCl_3,(C_2H_5)_2O,C_6H_6∼CCl_4,CCl_4∼CHCl_3,

&(C_2H_5)_2O∼CHCl_3.

(2) The quantities of flow, K, is a function of the mean pressure, p, and the K−p curve passes through a minimum point. The occurrence of a minimum point of mixtures is more remarkable than in the case cf simple gases.

(3) The quantities of flow of simple gases are satisfactorily expressed by

K=ap+γb,

where γ is a coefficient which becomes a constant at higher pressures (=0.9) or at very low pressures (=1.0), and varies from 0.9 to 1.0 at the intermediate conditions.

(4) The quantities of flow of mixtures are also expressed by a formula analogous to that of simple gases. The values of γ′ at higher pressures of the mixtures are constant for varying compositions of the same combination of components, but different from those for different combinations and simple gases. These values are also considered to depend on the chemical configurations of two components.

(5) The viscosities of the following mixtures have been calculated from the quantities of flow.

C_6H_6CCl_4, CCl_4∼CHCl_3,  (C_2H_5)_2O∼CHCl_3.

The mixture CCl4∼CHCl3 shows a maximum at about 50% of CHCl3 and the viscosity curves of the other two are nearly straight.
Effect of Water on the Potential of the Glass Electrode
Authors: Yoshimura Hisato
Published: July 2006

(1) When one surface of the membrane of a glass electrode is dried, the asymmetry potential is raised on that side against the other side, and the hydrogen electrode function is decreased. This membrane being kept submerged in water, the reverse effect is observed. These facts can be explained qualitatively by any of the latest theories concerning the glass electrode.

(2) The significance of preserving the glass electrode in water after its preparation, which is a generally accepted procedure in the use of the glass electrode, can be stated as follows: (i) It makes the hydrogen electrode function approach Nernst’s theoretical value, probably decreasing the cation effect on the potential of the glass electrode, (ii) it decreases the asymmetry potential, equalizing the electromotive nature of both the inner and outer surfaces of the electrode membrane, and (iii) it facilitates the equilibration of the potential after the electrode is mounted in a solution for test.
On the Silver Oxide Positive of the Alkaline Accumulator. II
Authors: Kinoshita Kyôji
Published: July 2006

(1) Further experimental investigations were made on the charge and discharge characteristics of the silver electrode of the cell which was constructed from the silver positive and the iron negative in KOH solution.

(2) Silver oxide positive gives very high value of the coefficient of utility of the active material.

(3) Discharge capacity and the utility coefficient are not seriously affected by the strength of the discharge current.

(4) The oxygen fixed in the active material in the charged state is consumed completely in the succeeding discharge.

(5) The amount of electricity charged is affected seriously by the strength of the charging current.

(6) These phenomena can well be explained by the following chemical reactions.

(Remark: Graphics omitted.)
A Theory of Surface Tension of Ternary Solutions
Authors: Ariyama Kyozo
Published: July 2006

The theories of surface tension of Debye-Hückel electrolyte can be divided into two main groups; one which is based on the assumption of the existence of the ‘image force’ near the boundary between water and air, and the other based on the calculation of surface free energy caused by the electrostatic force of ions. On the basis of experimental evidence on the surface tension of ternary solution, the theories of former category are shown to be unacceptable. Theories of Oka and also of Ariyama which belong to the latter category are applied to explain the surface tension of ternary solutions. Agreement with experiment is satisfactory.
A Note on the Osmotic Coefficient and the Activity Coefficient at the Surface
Authors: Ariyama Kyozo
Published: July 2006

The osmotic pressures and the activity coefficients for strong electrolyte solution and for solutions of mixture of electrolyte and non-electrolyte at the surface are calculated on the basis of Debye-Hückel theory. Some relations between the activity coefficients for two cases are given.
Synthesis of l-Talose
Authors: Fukunaga Shozo , Kubota Bennosuke
Published: July 2006

(1) l-Talose is formed by the reduction of l-talonic lactone obtained from l-galactonic acid by means of epimerisation. It is a colourless syrup with sweet taste having a specific rotation of −19.8° at 14°.

(2) l-Talonic acid (m.p. 137–138°, [α]D15° −18.2°) and l-talonic lactone (m.p. 133–134.5°, [α]D17° + 34.4°) are obtained.

(3) Brucine salt of l-talonic acid (m.p. 139–140°, [α]D14° −23.7°) is suited for the identification of the acid. The amide (m.p. 119–120.5°, [α]D18° + 13.3°) and the phenylhydrazide (m.p. 161–162°, [α]D13° + 26.0°) are also obtained.

(4) l-Galactonic acid is conveniently prepared from citrus pectic acid.
Distribution of Diethyl Tartrate between Ether and Aqueous Borate Solution and a Contribution to the Studies on the Equilibrium of the Boro-Diol Complex Formation
Authors: Tsuzuki Yojiro
Published: July 2006

(1) The distribution of diethyl tartrate between ether and water containing boric acid, borax or potassium metaborate (KBO2), has been measured.

(2) The results of the experiment on the system of ether–water have been found to follow simply the distribution law of Nernst.

(3) The distribution ratio in the system of ether-aqueous borate solution has been found to increase with the increasing electrolytic dissociation of borate, and this relation has been explained theoretically. The order of the magnitude of the distribution ratio to ether is water<borax<potassium metaborate.

(4) The equilibrium of boro-diol complex m the borate phase has been studied, and it has been shown that in the borate phase two complex compounds, i.e. those of mono-diol and di-diol types, must coexist, and the equilibrium constant (between ions) has been estimated.

(5) By the study of the temperature coefficient, the reaction of complex formation has been found to be exothermic and the heat of reaction has been estimated.

(6) The distribution of diethyl tartrate in the system of ether–water has been found indifferent to the addition of free boric acid, and this fact has been explained to be due to the insignificant dissociation of boric acid.
On the Silver Chromate Banding in Silicic Acid Gel
Authors: Isemura Toshizo
Published: July 2006

(1) The formation of silver chromate bands in silicic acid gel which was made by a usual method, has been described.

(2) By this procedure, the concentration of chromate is regulated at will, and distinct banding is formed.

(3) The hydrogen ion concentration of the gel has a profound influence on the formation of rhythmic bands of silver chromate.

(4) Dhar and Chatteriji’s theory and the membrane theory are not applicable.
On the Calcium Phosphate Banding in Silicic Acid Gel
Authors: Isemura Toshizo
Published: July 2006

(1) The formation of rhythmic precipitate of calcium phosphate in a silicic acid gel was described.

(2) The formation of this rhythmic precipitate was strongly affected by the hydrogen ion concentration of the gel.

(3) The effects of the concentrations of inner and outer electrolytes, and gel on this rhythmic precipitate, were studied.

(4) When the concentration of the inner electrolyte (CaCl2), was sufficiently great, no diffusion of the outer electrolyte into the gel took place but reversely calcium salt diffuse into the outer electrolyte solution and dendrities were formed in the outer solution.

(5) The effect of the existence of a third substance in the gel and in the diffusing electrolyte, were also investigated. The existence of it in a diffusing electrolyte had almost no influence but the existence in a gel had some effects, especially in the case where bromide and iodide of potassium were used as the third substance.
Extended Co-ordination Theory. I. Configuration of Simple Compounds of Typical Elements
Authors: Tsuchida Ryutaro
Published: July 2006

All the chemical linkages may be explained in terms of the co-ordinate covalence. By assuming that molecules and radical ions are built up by co-ordination of molecules, ions and electrons as ligands around central cations whose combining fields are given by sets of wave-functions, the configuration of all the simple as well as complex compounds could be readily found.
On the Nature of Foam. VI. Emulsion and Foam Formation of Ternary System, Ethyl Alcohol-Ethyl Ester-Water
Authors: Sasaki Tunetaka
Published: July 2006

(1) The mutual solubility curve, tie-lines and the foam stability of homogeneous and heterogeneous system of ethyl alcohol-ethyl ether-water (EEW) were measured. The diagram was established to show the relation between the foam stability and the composition. It shows two maxima of foam stability, one of which is situated along the mutual solubility curve, and the other is on the line of ethyl alcohol-water. The former is more remarkable in its magnitude than the latter as in the system of acetic acid-ethyl ether-water (AEW). The diagram shows the third maximum of foam stability but it is uncertain.

(2) Heterogeneous system of EEW is divided into three portions referring to the type of emulsion produced by shaking, namely, W-in-O region, O-in-W region and phase inversion zone. In W-in-O or O-in-W region, a system simply produces W-in-O or O-in-W emulsion respectively, whatever the modes of shaking, while in the phase inversion zone, a system occasionally produces both types of emulsion according to the two different modes of shaking. In the phase inversion zone, the tendency to produce W-in-0 emulsion gradually decreases and the tendency to produce O-in-W emulsion increases as a system changes in composition from those near W-in-O region to those near O-in-W region.

(3) Foam-nonfoam system can also be observed in this system as in AEW or acetic acid-benzene-water system. The region of its existence was determined.
Viscosity Effect on the Rate of Solution of Calcium Carbonate in Hydrochloric Acid
Authors: Tominaga Hitosi , Adzumi Hiroshi , Isobe Taro
Published: July 2006

The viscosity effect on the rate of reaction between marble and hydrochloric acid has been measured. The mechanism of the region of the first order reaction has been considered and the results show that the true chemical reaction on the marble surface and the diffusions of the reactant and reaction products concern in the same order in this reaction. The same conclusion is obtained from the experiments of changing the rotational velocity of the marble disk. The apparent heat of activation, which was calculated by Moelwyn-Hughes from the temperature coefficient of the rate, has been corrected by considering the viscosity effect.
Constitution of Two New Terpenes, Menogene and Menogerene (C10H16 and C10H14).–The Mechanism of Cyclisation of Citronellal and Citral
Authors: Horiuchi Riki , Otsuki Hiroshi , Okuda Osamu
Published: July 2006

One of the writers (Horiuchi) has proposed a mechanism of the cyclisation which occurs in treatment of citronellal and citral with sulphuric acid. The constitutions of two new terpenes, C10H16 and C10H14, produced by the reaction, are cleared up and they are named menogene and menogerene respectively.

The mechanism of cyclisation of citronellal and citral or generally of olefinic terpene aldehydes is largely cleared up. The intermediate state of these compounds in organisms is assumed. Not only the ring formation, but also the formation process of the terpenes is suggested. It is also shown that the semicyclic double bond is unstable and changes its position into the ring, taking the form of p-cymene.

Especially these two olefinic terpene aldehydes show the same behavior; that is, water is not needed for the ring formation; the terpenes are formed by dehydration of the hydrate; and the forms and positions of the double bonds are completely corresponding.

Their derivatives, menogene nitrosite and menogerene bromides, and 1-methyl-Δ-cyclohexadiene are formed and their natures are described.
On the Dialysis of Platinum-carbonyl Sol
Authors: Sano Isamu
Published: July 2006

The platinum-carbonyl sols of red colour prepared from 0.02 as well as 0.05% aqueous solutions of chloroplatinic acid were dialyzed in the atmosphere of carbon monoxide, as they would turn black to convert into platinum sols when treated in the air, until freed from chlorine ions.

The sols obtained through the process were just the same in appearance as well as in behaviour as they were formerly. This implies that the particles in the red sols, dialyzed or not, are fundamentally constituted from platinum and carbon monoxide or platinum-carbonyl.
Properties of Bismuth Oxide as an Active Material of Negative Electrode in Alkaline Storage Cell
Authors: Kinoshita Kyôji
Published: July 2006

(1) Negative electrode of the alkaline storage cell can be prepared using bismuth oxide as an active material, in pasted form or in pocketed form.

(2) The capacity of the electrode is improved greatly by mixing graphite powder to the active material, amounting the value 261 milliamperehour at highest per one gram of the oxide.

(3) It is thought to be probable, therefore, that the electrochemical properties of the electrode prepared from bismuth oxide, seems to have close connection with electrically resistant nature of the oxide.
Radium, Vanadium, Chromium and Molybdenum Contents of the Hot Springs of Yunohanazawa, and their Seasonal Variations
Authors: Kuroda Kazuo
Published: July 2006

(1) The radium, vanadium, chromium and molybdenum contents of the hot springs of Yunohanazawa, Hakone were determined.

(2) The seasonal variations of the amount of these elements were studied.
Zinc Content of the Hot Springs of Japan
Authors: Kuroda Kazuo
Published: July 2006

(1) The polarographic method was tested and found to be satisfactory for the determination of zinc in natural waters.

(2) The zinc content of a number of hot springs of Japan was polarographically estimated.

(3) The amount of zinc in sea water is considered to be less than 10 γ per litre.
Studies on Lignin. III. On the Lignin of Paulownia imperialis
Authors: Iwadare Koichi
Published: July 2006

Although paulownia wood is very soft, its lignin belongs to so-called hard-wood lignin, and it contains both syringyl and guaiacyl radicals. These facts are established by the measurements of the lignin content and of the methoxyl value of the paulownia wood lignin, and by the ethanolysis and oxidation with nitrobenzene.
Researches on the Chemical Reaction by Use of the Thermal Diffusion Apparatus of Clusius and Dickel. I. Thermal Polymerisation of Methane
Authors: Hirota Kozo
Published: July 2006

(1) A method of thermal polymerisation of methane proceeding in a thermal diffusion column of Clusius and Dickel has been described and discussed.

(2) By this method a good yield of condensed hydrocarbons and highly concentrated hydrogen gas have been obtained.

(3) Effects of the experimental conditions have been obtained.
Studies on the Derivatives of Biphenylene Oxide. V. Bromo-derivatives of Biphenylene Oxide
Authors: Yamashiro Seishi
Published: July 2006

For the purpose of confirming the constitution of the polybromo-compounds obtained directly from biphenylene oxide by bromination, the following experiments were performed by the present author:

(1) Verification of the formation of 2,3,6-trinitro- and 1,3,6,7- and 2,3,6,7-tetranitro-biphenylene oxides from 3,6-dinitrobiphenylene oxide and of the formation of 2,3,6-tribromo- and 1,3,6,7- and 2,3,6,7-tetrabromo-biphenylene oxides from 3,6-dibromobiphenylen oxide.

(2) Isolation of 2,7-dibromobiphenylene oxide from the bromination products of 2-bromobiphenylene oxide, and preparation of 1,3,6,8,-tetrabromobiphenylene oxide from 3,6-dibromo-1,8-dinitrobiphenylene oxide.

(3) Comparative studies on the characteristics and the absorption spectra of biphenylene oxide and its bromoderivatives.
Studies on the Derivatives of Biphenylene Oxide. VI. 4-Nitrobiphenylene Oxide and its Derivatives
Authors: Yamashiro Seishi
Published: July 2006

(1) 4-Nitrobiphenylene oxide was isolated in a pure state from the nitration products of biphenylene oxide and the amido, acetamido, dinitro, trinitro, tetranitro and bromonitro derivatives were prepared from it. The constitutions of the latter four derivatives were established.

(2) The physical properties, especially the absorption spectra, of those newly obtained compounds and the corresponding compounds derived from 1-, 2- and 3-nitrobiphenylene oxides were comparatively studied.
Studies on Reactions between Gas and Solid. VII Nitrogena-tion of Calcium Carbide and Its Kinetic Discussion
Authors: Aono Takeo
Published: July 2006

(1) From the experimental study of the nitrogenation of calcium carbide the author concluded its mechanism to be as follows:

(a) adsorptions of nitrogen on the carbide,

(b) formation of intermediate compound Ca(CN)2 temporarily,

(c) breaking of Ca(CN)2 into CaCN2 and C.

(2) Equations for this (gas-solid) reaction velocity were derived from above view. For constant temperature and pressure

(Remark: Graphics omitted.)

and for changing pressure

(Remark: Graphics omitted.)

(3) The coincidence of these equations with the experimental results were discussed.

(4) The heat of activation for the reaction of the adsorbed nitrogen and carbide to form calcium cyanide was calculated to be approximately 86 Cal./mol.
Hydrocarbons from Carbide (A) II. Non-Catalytic Polymerization under Ordinary Pressure. Hydrogen Systems and General Experimental Details
Authors: Negishi Ryoji , Kamiike Osamu
Published: July 2006

General experimental procedure, methods of analysis, and purification of materials have been given sufficiently in detail in order that the sources of difficulty and uncertainty in the results obtained not only in this paper but also in this series of investigations on the non-catalytic synthesis of hydrocarbon liquids directly from calcium carbide may be estimated.

Orientation and exploratory investigations have been made on hydrogen systems, and it has been found that a grain size of 1 to 2 mm, a saturation temperature of 80°C, and a reaction temperature of 340°C proved most suitable for the synthesis of liquid hydrocarbons under our experimental conditions.

The effects on the formations of the products of temperature have been discussed. These effects are intimately associated with the heat of reaction involving the carbide which is large.

The effects of the time of contact and of the grain size have been briefly mentioned in passing.
Hydrocarbons from Carbide (A) V. Non-catalytic Polymerization under Elevated Pressures. Comparison between Ordinary and Elevated Pressure Reactions
Authors: Negishi Ryoji , Kamiike Osamu
Published: July 2006

The effects on the character and yield of liquid products synthesized directly from calcium carbide under elevated pressures, of the species of gases, pressure, and temperature have been summarized. It has been found that the yield of liquid products increases with increasing total pressure of the system up to about 100 atmospheres and then decreases with further increase in the pressure.

The apparent characteristics of the products in carbon monoxide (or water gas) system seem different from the others, and an explanation for this has been given. As in the low pressure runs, carbon monoxide has rather harmful effects while, on the other hand, carbon dioxide has beneficial effects on the yield of liquid products.

There have been found slight differences in the yields and the properties of the products under elevated and ordinary pressures, and these differences have been explained as due rather to the effects of the time of contact and temperature than to any change in the mechanism of the polymerization reaction.

The limitations and the significance of the synthesis of hydrocarbon liquids directly from calcium carbide and several unique properties of the carbide which may be useful in organic syntheses have been pointed out and discussed.
An Empirical Equation for Calculating the Changes in the Boiling Points of Hydrocarbons with Small Changes in Pressure
Authors: Negishi Ryoji
Published: July 2006

An empirical relation,

(Remark: Graphics omitted.),

for calculating the change in the boiling point with a small change in pressure has been derived. It has been found that the equation is applicable to most of the hydrocarbons, with their boiling points ranging from −160 to 300°C., with a maximum deviation of about ±0.002.

A comparison of this equation with the others found in the literature has been made, and it has been found that the relation is just as accurate as some of the more complicated ones proposed.
Lead Content of the Calcareous Sinters
Authors: Kuroda Kazuo
Published: July 2006

The lead content of the calcareous sinter from the hot-springs of Yunomata in Northern Alps, Nagano Prefecture was estimated by the polarographic method.
Studies on the Derivatives of Biphenylene Oxide. VIII. Bromonitro-derivatives of Biphenylene Oxide
Authors: Yamashiro Seishi
Published: July 2006

(1) Twenty seven higher nitro-derivatives of 2- and 3-bromo-, 2,6-, 3,6- and 1,8-dibromo-, 2,3,6-tribromo-, and 1,3,6,7- and 2,3,6,7-tetrabromobiphenylene oxides were newly obtained by nitrating the corresponding lower nitro-derivatives, and their constitutions were established.

(2) The absorption curves of those bromonitro-compounds were compared with each other, and also with those of the corresponding nitrobiphenylene oxides, to the confirmation of their constitutions as a consequence.

(3) In the nitration of the bromo- and bromonitro-biphenylene oxides, it was found that when the relative arrangements of the substituents at the 2- and 3-positions to the 1-position are the same as those of the same substituents at the 3- and 2-positions to the 4-position, the introduction of the nitro group more readily takes place at the 4-position than at the 1-position.
The Formation of d-Ribomethylose
Authors: Iwadare Koichi
Published: July 2006

d-Allomethylose is obtained from l-rhamnose by a little modification of Levene’s method. And d-ribomethylse is prepared from d-allomethylose by Wohl’s method of degradation, obtaining on the way d-allomethyloxime (melting point, 146–146.5°, and [α]D18, +54°, 6 minutes after dissolution and −4° in equilibrium), tetracetyl d-allomethylonic nitrile (melting point 166.5∼167°), and d-ribomethylose diacetamide (melting point, 191°, and [α]D18, +7.4°). Equilibrium specific rotation, [α]D20, of d-ribomethylose is found to be +20°.
A Theory of the Ludwig-Soret Effect
Authors: Hirota Kozo , Kimura Osamu
Published: July 2006

A mechanism of the Ludwig-Soret effect has been proposed and formulated after the recent theory of viscosity and diffusion. The important assumption therein adopted is that the reaction rate formula can be applied even in the systems which have a temperature gradient.

Soret coefficient and thermal diffusion coefficient have been calculated theoretically and the coincidence of the calculated values with the observed has been shown quite satisfactory.
Synthesis of Tertiary Butyl Alcohol by the Hydration of Isobutylene. IV. Some Attempts for the Confirmation of the Formation of Tertiary Butyl Sulphates, and Discussions on the Reaction Mechanism
Authors: Katuno Masaharu
Published: July 2006

1. The confirmation of tert-C4H9OSO3H, which has been assumed as the intermediate compound in the hydration and polymerisation of isobutylene with sulphuric acid, has been attempted in the form of sodium or barium salts though with negative results.

2. The reaction mechanism of the hydration reaction of isobutylene with sulphuric acid has been discussed. Experimental results can be explained by the assumption that tert-C4H9OSO3H formed is very reactive to undergo rapid hydrolysis to establish the following equilibrium rapidly.

(Remark: Graphics omitted.)
Studies on Nickel and Cobalt in Mineral Springs. II. Nickel and Cobalt Contents of Tentoku Mineral Spring, Saga Prefecture
Authors: Tanaka Nobuyuki
Published: July 2006

The determinations of nickel, cobalt and the major constituents in Tentoku Mineral Spring, Saga Prefecture, typical of the acid vitriol springs in Japan, have bee made. The result is that this spring contains such a remarkable amount both of nickel and cobalt that it proves to be the richest in our country in either element, showing 9.38 mg. Ni/l. and 2.19 mg. Co/l.

The distributions of these two elements between the filtrate and the precipitate have been investigated. Either of these mostly remains in the filtrate and partly migrates to the precipitate. In this regard a difference between nickel and cobalt, if it could be found, seems to be a matter of degree, that is, a problem as to which element has closer affinity to the precipitate of ferric hydroxide.
Studies on the Equilibrium between Dilute Solution and Solute Vapour. III. Calculation of the Evaporation and Dissolution Velocity
Authors: Uhara Ituro
Published: July 2006

(1) The absolute rate method was applied to the dissolution and evaporation processes of the solute vapour in the solution.

(2) The energy of the transition state was estimated from the temperature coefficient of condensation coefficient (α) of iodine experimentally determined. The energy is not maximum at the transition state as is usually assumed in the transition state method.

(3) α, evaporation probability (β1) and entropy of dissolution (ΔS) were calculated for simple cases by means of simple models of the transition state and solution. For complex cases only qualitative explanation is possible.

(4) α of very light gases may be of the order of 10−2.
SOME NEW METALLO-ORGANIC OXONIUM SALTS
Authors: Harada Taichi
Published: July 2006

The formation of the compound, ((CH3)3 Sn)2O·(CH3)3Sn X, H2O, from trimethyltin halide by the action of sunlight in the presence of air have been studied and the mechanisms of the formation were interpreted. Identical products have been prepared by the following methods: (A) By oxidizing of trimethyltin group along with trimethyltin halide in benzene solution in the dark, and (B) by treating two molecular proportions of trimethyltin hydroxide with one molecular proportion of trimethyltin halide in hot benzene solution.

2. Compounds exhibit salt–like properties, being readily soluble in water, alcohol, acetone and liquid ammonia, and insoluble in benzene and ether. They conduct electric current appreciably in their solutions.

3. When the liquid ammonia solution is treated with an equivalent amount of metallic sodium in respect to the iodine trimethyltin oxide, ((CH3)3Sn)2O, and trimethyltin group, (CH3)3Sn, are produced.

4. Compounds of the type, ((CH3)3Sn)2O·HX, H2O, have been prepared by treating of one molecular proportion of trimethyltin hydroxide with one molecular proportion trimethyltin halide or one molecular proportion of trimethyltin oxide with one molecular proportion of halogen acid under suitable conditions.

5. They are salt–like properties, being soluble in water and alcohol, and insoluble in nonionizing solvents such as benzene and ether.

6. Their melting points and stabilities are higher than those of the type, ((CH3)3Sn)2O·(CH3)3Sn X, H2O.
SPECTROCHEMICAL STUDIES OF HYDROXYAZO-COMPOUNDS. PART V
Authors: Uemura Taku , Tabei Shozo
Published: July 2006

(1) Tautomeric transformations may take place in these hydroxyazo-compounds.

(2) We may assign A (azo)-form to the neutral solution and R (red)-form to the alkaline.

(3) In general, one band can be shown in the absorption curves, except when the hydroxyl-group takes an ortho-position with regard to the azo-group.

(4) Hydroxyl- and nitro-radicals in para-position with respect to the azo-group are most effective in the absorption curve.

(5) The methyl-group has generally a hyperchromic influence upon the non-methylated compounds.
THE VISCOSITY OF LIQUIDS ABOVE THEIR BOILING POINTS. PART I
Authors: Titani Toshizo
Published: July 2006

1. The viscosities of methyl-acetate and fluorobenzene were determined above their boiling points after the method described by A. Heydweiller.

2. To overcome several difficulties which arise from the use of his apparatus, a new viscosimeter was devised.

3. By means of this apparatus, the viscosities of carbon-tetrachloride, chlorobenzene and ethyl alcohol were determined above their boiling points.
On the Determination of Copper by the Polarographic Method
Authors: Ohashi Shigeru
Published: July 2006

A new method for the determination of copper with the dropping mercury electrode was studied and the following regulating solution was used: 1 mol sodium potassium tartrate and 1 normal sodium bydroxide. By this method copper can be determined in the presence of large ammounts of iron.
Hydrogenation of Furfural and Furfuryl Alcohol. IV. Hydrogenation of Furfural into Furfaryl (Tetrahydrofurfuryl) Alcohol by the Combination of Copper Chromium Oxide Catalyst and Nickel Kieselguhr Catalyst
Authors: Katuno Masaharu
Published: July 2006

1. Furfural was hydrogenated into furfuryl alcohol by using copper chromium oxide catalyst under high pressure. Then the product was further hydrogenated by adding nickel kieselguhr catalyst, without separation and purification of furfuryl alcohol. The hydrogenation proceeded rapidly and furfaryl alcohol about 83–84% of the theoretical yield was obtained.

2. Furfural was hydrgenated by using copper chromium oxide catalyst and nickel kieselguhr catalyst, which were prepared separately before use. The hydrogenation proceeded rapidly, and furfaryl alcohol, (about 74∼79% of the theoretical yield) was obtained, which is slightly lower than in the above procedure.

3. The mixture of Cu(OH)(NH4)(CrO4) and nickelcarbonate kieselguhr, mixed mechanically or in the state of precipitates, was used for the hydrogenation of furfural, after reducing it with hydrogen or after thermal decomposition without reduction. The results was less satisfactory compared with the above two procedures.
Studies on Nitrate Reductase. III
Authors: Sato Ryo , Egami Fujio
Published: July 2006

The effects of various inhibitors on nitrate reductase have been investigated and some spectroscopic observations have been made to elucidate the chemical nature of nitrate reductase. From these studies it becomes very probable that cytochrome b of Bac. coli type is identical with nitrate reductase.
Fundamental Studies on the Current-Voltage Curve in Polarography. I
Authors: Tanaka Nobuyuki , Tamamushi Reita
Published: July 2006

The formula of the current-voltage curve in polarography has been derived from the view-point of chemical kinetics and independently of the Nernst’s equation. As a result, it has been clearly shown that if the condition of the diffusion-control is fulfilled the formula which had been derived from the Nernst’s equation has been obtained in the various types of the electrode reaction. Of these types both the oxidation-reduction of the simple (or hydrated) metal ions and the deposition of the metals from the simple (or hydrated) metal ions have been dealt with in the present paper.

It is also suggested that the “ irreversible wave” which cannot be treated theoretically based on the Nernst’s equation can possibly be dealt with by the similar derivation as mentioned here.

The authors take this opportunity of acknowledging their gratitude to Director San-ichiro Mizushima for his kind advice and encouragement throughout this study. The cost of this research has been defrayed from the Scientific Research Encouragement Grant from the Department of Education, to which the authors’ thanks are due.
On the Equilibrium of the Radioactive Elements in the Hydrosphere. VI. Radioactivity Measurement of Natural Waters with the Geiger-Müller Counter
Authors: Kuroda Kazuo
Published: July 2006

The radioactivity of the natural water was measured with the Geiger-Müller counter. The relationship between the radon content of the thermal springs of Misasa and the number of counts was studied. The increase of β and γ radioactivity of fresh mineral waters was observed.
Inhibitory Effect of Cyanine- and Styryl-Dyes upon Cholinesterase. I
Authors: Hase Eiji , Mizuno Yoshihisa , Katayanagi Masujiro
Published: July 2006

(1) It was found that a number of cyanine- and styryl-dyes has a strong inhibitory action upon cholinesterase.

(2) Both the specific and non-specific cholinesterase are inhibited by the subtances, the latter being probably more susceptible than the former.

(3) The substances have no appreciable effects upon the liver esterase. With the esterase in horse serum, even a slight acceleration of the activity was observed under the influence of some dyes investigated.

(4) For some related members of styryl-dyes, a certain relationship between chemical constitution and their inhibitory effects upon cholinesterase could be found.
Fundamental Research on Anodic Reaction. II. Activation Energy of Anodic Oxygen-producing Reaction on Some Electrode Materials in Aqueous Solution of n/10 Sodium Hydroxide
Authors: Yoneda Yukio
Published: July 2006

Activation energies of anodic oxygen-producing reaction on electrode of platinum, magnetite, or natural graphite were measured in aqueous solution of n/10 NaOH under stirring by the stream of oxygen gas, at temperature from about 25° to 65°C. On platinum anode, overvoltage was measured by two methods, (i) by the ordinary method just after 30 minutes from the time of closing the electric circuit, and (ii) by the oscillographic method. The activation energy calculated herefrom was found 15.9 ±2.0 kcals. by (i) method, and 13.8 ±0.6 kcals. by (ii) method. On magnetite and natural graphite, overvoltage was measured by (iii) ordinary method at the stationary state which was obtained after a few minutes. Activation energy of the former was found to be 26.2 ±3.2 kcals., and that of the latter is not obtained. The activation energy on platinum by oscillographic method is consistent with that measured by F. P. Bowden in the aqueous solution of n/5 H2SO4, which is 13–14 kcals. after being corrected about the temperature coefficient of oxygen equilibrium potential. These facts suggest that the anodic oxygenproducing reaction on platinum proceeds through the same ratedetermining step both in acid and alkaline solutions, and the mechanism is rather different on platinum from the one on magnetite.