bluuebunny/crossref_metadata_2025 huggingface dataset:
The Nuclear Magnetic Resonance Spectra of Some 4,6-Disubstituted o-Cresols
Authors: Kondo Michio
Published: July 2006

The nuclear magnetic resonance spectra of seven 4,6-disubstituted o-cresols (4,6-dinitro-, 4-nitro-6-bromo-, 4,6-dichloro-, 4,6-dibromo-, 4,6-diiodo-, 4,6-dimethyl-, and α, 4,6-tribromo-o-cresol) have been examined in dilute deuterochloroform solutions at 60 Mc./sec.

The observed chemical shifts of the ring protons 3 and 5 of 4,6-disubstituted o-cresols are in good agreement with the values calculated from the shielding parameters of substituents by assuming the additivity rule.

The spin-spin coupling constant between two ring protons is proportional to the sum of the electronegativities of the substituents 4 and 6.

There are weak long-range couplings between the methyl and ring protons. It has been suggested that hyperconjugation contributes to thesee couplings.
Studies on Amino-hexoses. VIII. The Fischer Synthesis of Methyl d-Glucosaminides
Authors: Matsushima Yoshio , Miyazaki Tsuyoshi
Published: July 2006

The direct synthesis of methyl d-glucosaminides by proton catalysis using a strong cation exchanger has been investigated. The formation of the two anomeric pyranosides has been proved unambiguously. Also, the two anomeric furanosides, which have been obtained in an unsatisfactory purity, have been inferred, according to their physical constants, to have formed in the glycosidation reaction.
The Electrolytic Formation and Dissolution of the Oxide Layer on Rhodium in an Acid Solution
Authors: Shibata Shigeo
Published: July 2006

Surface oxides on the smooth rhodium electrode have been characterized by anodic oxidation and by cathodic stripping with a constant current under various conditions.

The oxidation reaction of the surface should consist of three stages with a characteristic potential region; the adsorption of OH, the formation of an oxide, Rh–O, and, finally, the formation of a higher oxide, Rh2O3. The oxide thus formed is cathodically reduced step-by-step in two different potential regions. These mechanisms are supported by the experimental data of the charging curves taken under various conditions, the corrosion by the square-wave alternating-current electrolysis, and the variation in the electrode capacity during the electrolysis.
The Reaction of Dimethyltin Dichloride with Carboxylic Acids and Phenols in an Aqueous Solution
Authors: O’hara Mitsuaki , Okawara Rokuro , Nakamura Yoshiaki
Published: July 2006

The reactions of dimethyltin dichloride with carboxylic acids and phenols in aqueous solution have been described, and ten new compounds reported. In many cases tetramethyl-1,3-di(substituted)distannoxanes are formed in good yields by adding such deprotonating reagents as concentrated aqueous ammonia. In other cases, simple dimethyltin derivatives can be obtained without deprotonating reagents.
The Absorption Spectra of Naphthalene Sulfonic Acid Derivatives
Authors: Tanizaki Yoshié , Inoué Hiroyasu , Ando Noboru
Published: July 2006

1) The absorption spectra of some naphthalene sulfonic acid derivatives have been determined in various pH solutions.

2) The remarkable spectral change revealed by the variation in pH value can be interpreted in terms of the process of the proton association and dissociation of the functional groups.

3) The pH region in which the process takes place is characteristic of the kinds, –NH2, –OH, and the number of the functional groups and their locations on the naphthalene skeleton.

4) The relative pH regions have been explained in outline by taking into account the effects of the sulfonic group, the intramolecular hydrogen bond formed between the functional groups, and the resonance of the functional group to the link.

5) The band assignment concerning the transition direction of the derivatives has been decided; the first and the second band correspond, respectively, to the 1La and 1Bb of naphthalene.

6) The order of the magnitude of the substitution effect has been clarified as –NH3+< –OH<–NH2<–O−.
Studies of the Stability of Cobalt Ferrocyanide Sol in Ultrasonic Field. The Ultrasonic Dispersion of Cobalt Ferrocyanide
Authors: Prakash Satya , Prakash Om , Prakash Sheo
Published: July 2006

A negatively-charged cobalt ferrocyanide sol has been prepared ultrasonically subjecting the washed precipitate of cobalt ferrocyanide and distilled water to ultrasonic waves. The amount of dispersion increases with the time of exposure. The sol is rendered more stable in an ultrasonic field in the presence as well as in the absence of oxygen. The enhanced stability has been attributed to the increase in hydroxyl ions in the medium as a result of the hydrolysis of cobalt ferrocyanide sol. The stability, pH and specific conductivity values are very little affected in the presence of methanol, ethanol and acetone. The inhibition is due to the suppression of cavitation and to a lesser energy release on the collapse of cavitational bubbles.
The Anomalous Behavior of Some 2,6-Disubstituted Iodobenzenes in the Jacobsen Reaction
Authors: Suzuki Hitomi , Maruyama Kazuhiro , Goto Ryozo
Published: July 2006

Some 2,6-disubstituted iodobenzenes undergo an anomalous Jacobsen reaction and so afford none of the expected vicinal, but only symmetrical diiodo products. This anomaly has been investigated using 2-iodo-m-xylene as the reagent. The reaction has been found to proceed mainly through the rapid isomerization of 2-iodo-m-xylene to the 4-iodo isomer, followed by the normal disproportionation to 4,6-diiodo-m-xylene. A possible mechanism has also been proposed on the basis of the results obtained.
Solvent Extraction Studies of Tellurium(IV) with Dithizone
Authors: Mabuchi Hisao , Okada Isao
Published: July 2006

Tellurium(IV) can be extracted into organic layers with dithizone. The analysis of the experimental results suggests, as the main process of extraction:

Te(OH)3+ (or TeOOH+) (aq.)+2H2Dz (org.)

=Te(OH)2(HDz)2 (or TeO(HDz)2) (org.)

+H+(aq.)+xH2O (aq.)

The spectrophotometric measurements show that tellurium dithizonate in carbon tetrachloride has an absorption maximum at 427 mμ, where the molar extinction coefficient is 4.10×104  m−1cm−1.
Oxidation of Alcohols with t-Butyl Chromate. III. The Oxidation of Alicyclic Alcohols
Authors: Suga Takayuki , Matsuura Tamon
Published: July 2006

1) The t-butyl chromate oxidation of myrtenol gave no ester, but it did give the corresponding aldehyde as the main product, while the oxidation of cyclohexylcarbinol gave a mixture of the corresponding aldehyde, acid and ester in comparable yields.

2) A similar oxidation of cyclohexanol afforded the corresponding ketone in a high yield, while the oxidation of cyclohexane-trans-1,2-diol produced no corresponding diketone, but it did produce the glycol fission product and a cyclic ester such as trans-1,2-adipoxycyclohexane (a new compound). On the other hand, p-menthane-trans-3,4-diol yielded only the corresponding hydroxyketone in a good yield.
The Reaction of 3,5-Dibromo-4-hydroxybenzenesulfonyl Chloride with Weak Bases (The Question of the “Quinoid Sulfene” Intermediate)
Authors: Oae Shigeru , Kiritani Reiko
Published: July 2006

The formation of the “quinoid sulfene” intermediate, II, during the reaction between 3,5-dibromo-4-hydroxybenzenesulfonyl chloride and a weak base has been investigated by following the ultraviolet spectra of the reaction mixture. It has been suggested that the colorless precipitate formed as the final product of the reaction is an oligomer and has structure V.
The Isocyanurates. I. A Novel Method of Synthesizing Trialkyl Isocyanurates
Authors: Fukui Kenichi , Tanimoto Fumio , Kitano Hisao
Published: July 2006

Reactions of alkyl halides with potassium cyanate have been carried out in several aprotic solvents. Dimethylformamide and dimethyl sulfoxide have been proved to play a superior role as aprotic solvents in the displacement reaction and also in the subsequent trimerization of the isocyanates. Several trialkyl isocyanurates have been obtained in yields better than those of the other known methods.

From 2-alkoxyethyl halides and 2-vinyloxyethyl chloride respectively, tris-(2-alkoxyethyl) isocyanurates and tris-(2-vinyloxyethyl) isocyanurate have been synthesized.

The presence of water in the reaction mixture results in the formation of 1,3-dialkyl ureas, consequently decreasing the yield of isocyanurates.
A Study of Concentrated Solutions of Mixed Electrolytes. Ultrasonic Velocities and Viscosities of Mixtures of Aqueous Solutions of Potassium and Sodium Chlorides at High Concentrations
Authors: Kuppusami J , Lakshmanan A S , Lakshminarayanan R , Rajaram N , Suryanarayana C V
Published: July 2006

The electrical conductance of mixtures of aqueous solutions of potassium and sodium chlorides has been studied by previous workers. However, no valid explanation has been given for the conductance behaviour of the mixtures.

We have reported herein the results of our ultrasonic of the viscometric studies of mixtures. Even now the hydration numbers and the viscosity variation are inadequate to explain the conductance behaviour of the mixtures. We have observed that all the mixtures follow the exponential relation, η=AeBμ, where A and B are constants; η the viscosity of the mixture, and μ, the ionic stregth.
Studies of Thermosetting Resin. I. The Infrared Analysis of Cured Epoxy Resins
Authors: Sugita Tadao , Ito Mitsuko
Published: July 2006

To pulverize the cured hard resins for the infrared KBr technique, the method using a file is very simple and convenient.

From the infrared spectra of the powder of cured epoxy resins using the KBr-pellet technique, the curing agent used can be readily identified by type whether it is an amine or an acid-anhydride type by the absence or presence of the carbonyl absorption band.

Furthermore, in the case of the acid anhydride-cured epoxy resins, the acid anhydride used as the curing agent can be identified by type from the spectra of the resin pyrolyzate. Namely, PA, THPA, EMTHPA, HET, and DDSA may be identified immediately from the spectra of pyrolyzates between room temperature and 300°C, and HHPA, from the spectrum of the pyrolyzate between 300 and 350°C. The results of these experiments are summarized in Table II.

PMDA used as a curing agent can not be so straightforwardly identified as in the other cases, but even this may be identified by a comparison of the spectra of the pyrolyzates of PMDA-cured resin with those of the pyrolyzates of each resin.
Studies of the Organic Reaction of Metal Carbonyl. VII. The Acceleration Effect of the Addition of Inorganic Compounds on the Reaction of Olefin Oxide with Cobalt Hydrocarbonyl
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa , Masada Hiromitsu
Published: July 2006

The reaction of olefin oxide with cobalt hydrocarbonyl in the presence of inorganic (and organic) additives has been investigated.

1) The addition of relatively small amounts of various compounds of copper and silver promote the carbonylation of propylene oxide. The order of the promoting effect of these compounds is Cu2O, 70>CuO, 6O>(AlCl3, 30) >Ag2O, 27>CuCl2, CuCl and Cul, 20>CuCN, 15>AgCl, 9>Cu powder, 4>None, 1 (the numbers indicating the relative rates of the gas absorption at the early stage of the reaction). Among these, cuprous oxide has the largest effect. The amount of cuprous oxide necessary for this effect is only about 0.005 mol./mol. HCo(CO)4. β-Hydroxy-/n-butyrate has been the main reaction product obtained. On the other hand, chlorides of zinc, nickel, ferric, potassium, magnesium, palladium and titanium have no promoting effect on the reaction.

2) The combination of cuprous halide (and oxide) with various organic additives, which also have a promoting effect, has a synergistic effect on the reaction of propylene oxide.

3) The reaction of epichlorohydrin is also promoted by the addition of cuprous oxide. However, in this case cuprous oxide combined with ethyl alcohol has a retardation effect.
The Cation Exchange Investigation of Scandium Acetate and Sulfate Systems
Authors: Tateda Akira
Published: July 2006

Ion exchange equilibria between the cation exchange resin, Amberlite IR-120, and an aqueous solution containing a small concentration of scandium ions and a relatively large concentration of acetate or sulfate ions have been measured at a constant ionic strength of μ=0.5 and at 25°C. The values of the formation constants of the complexes in solution have been calculated by the application of the Fronaeus method3) and by the graphical method.5).In the case of the acetate system, at an acetate ion concentration [Ac] ≤14.5×10−2mol./l. and pH 4.5, species with scandium to ligand ratios of 1:1, 1:2 and 1:3 seem to be formed. However, since scandium exists mainly in two ionic species, Sc3+ and Sc(OH)2+, in the solution, the chemical formulae can not be determined; therefore, the formation constants have been estimated for the addition of each formation constant of two complexes with the same ligand ratio, Sc(Ac)j3−j and Sc(OH) (Ac)j2−j. The values of Bj=(βj+(βj′*K1[H+]−1) were B1=22±10 mol−1., B2=(15±7)×102 mol−2l2 and B3=(11±3)×103 mol−3l3 at pH 4.5. In the case of the sulfate system, three complex ions were formed at a sulfate ion concentration of [SO42−]≤4.65×10−2 mol./l. and pH 2.7 : Sc(SO42−)+, Sc(SO42−)2− and Sc(SO42−)33−. The formation constants were β1=46±5 mol−11., β2=(11±6)×102 mol−2l2 and β3−=(10±7)×103 mol−3l3.
Quinoxaline Derivatives. VII. The Mechanism of the Formation of 6-Chloro-1,2,3,4,2′,3′-hexahydro-4,1′-dimethyl-3,2′-dioxoquinoxaline-2-spiro-3′-indole from a Quinoxaline N-Oxide Derivative by Nucleophilic Chlorination
Authors: Ahmad Yusuf , Habib M S , Iqbal M , Qureshi M I , Ziauddin
Published: July 2006

The compound IVb named in the title has been obtained by an unambiguous route. It has been shown to be identical with the product of the reaction of the N-oxide (Ia) with ethanolic hydrogen chloride. Clark-Lewis and Katekar’s mechanism for the nucleophilic chlorination in the latter case has been discussed, and a modified mechanism proposed.

Isomeric 7-chloro-spiro-indole (IVc) has also been obtained by the rearrangement of the anilide IIIc. Similarly, the anilide IXi gives spiro-indole (IVc; H for Me’).

The anilides IIIb and IIIc give normal N-oxides Ib and Ic, which, with concentrated sulphuric acid, decompose and afford the amines IIb and IIc. IXi, instead of giving its N-oxide, yields 6-chloro-2,3-dihydroxyquinoxaline.
The Rapid Solvent Extraction and Simultaneous Spectrophotometric Determination of Palladium with TTA - Methyl Propyl Ketone
Authors: Rangnekar Asha V , Khopkar S M
Published: July 2006

A spectrophotometric method has been developed for the determination of palladium-(II) at microgram levels; the method is based on the colour reaction with 2-thenoyltrifluoroacetone (TTA) in methyl propyl ketone (MPK). The bright orange-yellow-coloured palladium(II)-TTA chelate solution follows Beer’s law at 430 mμ over the 0.6–6.0 γ range of palladium(II) per millilitre. At pH values from 3.4 to 4.9, about 80% or more of palladium(II) is removed from an aqueous solution of TTA-MPK in a single extraction. The coloured system is stable for 72 hr. It can tolerate lead(II), thallium(I), cadmium(II), antimony(III), bismuth(III), platinum(IV), aluminium(III), zinc(II), nickel(II), zirconium-(IV), phosphate, chromate, acetate and sulphate, whereas tin(IV), manganese(II), cobalt(II), ascorbate, oxalate, citrate, tartarate and cyanide seriously interfere. Mercury(II), thorium(IV), calcium(II), strontium(II), barium(II), magnesium(II), vanadate and tungstate are moderately tolerated. The method is accurate and reproducible to within ±1.5%, and it offers a simple procedure for the simultaneous extraction and spectrophotometric determination of palladium(II).
Adsorption Measurements during the Synthesis of Methanol at Lower Pressures
Authors: Tsuchiya Susumu , Shiba Tadao
Published: July 2006

Adsorption has been studied on a three component methanol synthesis catalyst during the synthesis of methanol in a closed circulating system. It has been shown that the adsorption of hydrogen and carbon monoxide are both enhanced by the presence of the other. The composition of the adsorbed phase has scarcely been affected at all by the ratio of the partial pressure of hydrogen to carbon monoxide, and the formation of surface complex has been suggested. The rate-determining step of the synthesis of methanol has been suggested to be the process of the Eley-Rideal type hydrogenation of the surface complex.
The Electronic Spectra of Aniline and N-Methylaniline Adsorbed on Aluminum Chloride. II. The Theoretical Treatment
Authors: Sato Hiroyasu , Nagakura Saburo , Hirota Kozo
Published: July 2006

The electronic spectra of aniline and N-methylaniline adsorbed on aluminum chloride have been examined by the LCMO method and have been compared with those of gaseous aniline, N-methylaniline, toluene and ethylbenzene. All of these molecules can be treated by the intramolecular charge-transfer model. In order for us to be able to interpret the spectra from the LCMO point of view, the ionization potential of the electron donating group in aniline and N-methylaniline molecules should rise upon adsorption on aluminum chloride.
Small-angle Scattering from Methane, Ammonia and Water by Fast Electrons
Authors: Iijima Takao , Bonham Russell A , Tavard Claude , Roux Monique , Cornille Marguerite
Published: July 2006

The total differential scattering cross sections for the 40 kV. electron from the methane, ammonia and water molecules obtained experimentally over the 1≤s≤8 s range have been compared with the theoretical results. Good agreement with the theoretical results have been obtained in the case of methane. In the cases of ammonia and water the results are in qualitative agreement with the theoretical predictions, but uncertainties in both the theory and experiment prevent a detailed comparison from being made in these cases.
The Adsorption of Copper(II), Dichromate(II) and Oxalate(II) by Different Samples of Precipitated Hydrous Beryllium Oxide
Authors: Dutta Rup
Published: July 2006

Three samples, A, B and C, of hydrous beryllium oxide were prepared by adding different amounts of alkali to a fixed volume of a beryllium sulfate solution. Sample A prepared with an equivalent amount of alkali, sample B prepared with a 10% deficient amount of alkali, sample C prepared with a 10% excess amount of alkali.

These samples were washed thoroughly and allowed to age for a month. The adsorption capacities of these samples for the ions copper-(II), oxalate(II) and dichromate(II) were then studied. The adsorption of copper (II) by different samples was found to be in the order B>A>C, whereas in the case of oxalate and dichromate the order of adsorption, is C>A>B.
The Synthesis of Cyclo-pentaglycyl-l-lysyl and Its Hydrolysis by Trypsin
Authors: Ohno Motonori , Izumiya Nobuo
Published: July 2006

A cyclic hexapeptide, cyclo-pentaglycyl-l-lysyl hydrochloride (IIL), has been synthesized in an attempt to obtain fundamental information about the syntheses of cyclic peptides; it has also been subjected to the action of trypsin.

p-Methoxybenzyloxycarbonyltriglycyl-ε-benzyloxycarbonyl-l-lysylglycylglycine (XX) has been prepared by the saponification of the di-N-blocked hexapeptide ester which had been obtained by the condensation of p-methoxybenzyloxycarbonyltriglycyl-ε-benzyloxycarbonyl-l-lysine azide with the glycylglycine benzyl ester. XX has been converted to the relevant p-nitrophenyl ester by the action of di-p-nitrophenyl sulflte, and, after the removal of the p-methoxybenzyloxycarbonyl group with trifluoroacetic acid, the hexapeptide p-nitrophenyl ester has been transformed, by means of a large amount of pyridine, to the cyclic benzyl-oxycarbonyl-substituted hexapeptide. It has then been hydrogenolyzed in the presence of palladium black to furnish the desired product, IIL.

Several different synthetic methods for obtaining IIL have been adopted. However, they are not satisfactory with regard to the optical purity of the l-lysine residue or the yield.

It has been observed that IIL is completely hydrolyzed to pentaglycyl-l-lysine by trypsin. This appears to be the first example of how trypsin can hydrolyze a cyclic peptide. A smaller cyclic peptide, glycyl-l-lysine anhydride, could not be hydrolyzed.
The Solution State of Cationic Polysoap Derived from Polyallyl Chloride
Authors: Ishigami Yutaka , Narasaki Hideo
Published: July 2006

Cationic polysoap (SP-100, mol. wt. 2770), consisting of a short polymer chain with -chemically-attached soap-like groups, has been prepared by quaternizing N-dodecylpiperidine with polyallyl chloride (mol. wt. 647). Some properties of the aqueous solution of SP-100 has been investigated by the light-scattering and surface-tension methods in the absence of and in the presence of sodium chloride.

We have found that the solution of such a polysoap exhibited the CMC value and that the concentration was 3.64×10−4 mol./l. (light scattering).

When the logarithmic relation between the CMC and the total gegen ion concentration was plotted, the curve thus obtained could be divided into two regions. Namely, the curve was almost flat at lower total gegen ion concentrations, followed by a depressed portion.

The micellar weight of SP-100 was 18800 in water and 32300 in a 0.3 m sodium chloride solution. The charges of SP-100 in aqueous solutions were calculated from the slope of the Debye plots by the derived equation of Princen and Mysels; on the basis of these results, the micellar charge of SP-100 in water is quite small.

The surface excess (Γ2), together with the corresponding surface area (A), of SP-100 at the air-solution interface has been calculated from the slopes of the surface tension vs. the logarithm of polysoap concentration curve slightly below the CMC by applying the Gibbs equation. The Γ2 value thus obtained was 3.78×10−10mol./cm2, while A was 44Å2/mol. The Γ2 value of SP-100 in mol./cm2 was of nearly the same order of magnitude as those of ionic monosoaps.
The Interaction of Cumulene Systems with Organometallic π-Complexes. III. Iron Carbonyl Complexes of Hexapentaene and of Tetra- and Dimethylbutatriene
Authors: Nakamura Akira
Published: July 2006

The reaction of 1,6-dihalohexadiyne-2,4 with tri-iron dodecacarbonyl in the presence of an excess of zinc powder have given a hexapentaene iron carbonyl complex, C6H4Fe3(CO)7−8, as deep purple-red, air-stable crystals in a 1.2% yield. Essentially the same reaction using methyl-substituted 1,4-dichlorobutyne-2 have given substituted butatriene iron carbonyl complexes,(R1R2C=C=C=CR1R2)Fe2(CO)5, where R1 = R2 = CH3 (V), R1 = H, and R2 = CH3(IV), in low yields. The vibrational, electronic and NMR spectra of these new complexes have been discussed in connection with their structures.
The Absorption Spectrum of the Cobalt(II) Ion Catalyst in the Reaction of Methanol with Carbon Monoxide and Hydrogen under a High Pressure
Authors: Mizoroki Tsutomu , Nakayama Mikitake
Published: July 2006

The absorption spectra during the course of the reaction of methanol with carbon monoxidehydrogen mixtures in the presence of a mixture of cobalt (II) acetate and sodium iodide as the catalyst under high temperatures and pressures (180–185°C, 200–220kg./cm2) have been taken, using an automatic recording spectrophotometer and special autoclave made of Ti-Mn alloy and a couple of thick pieces of quartz glass. Whenever the reaction starts, the absorption corresponding to that of [Co-(AcO4]2− goes on decreasing, while that corresponding to [CoI4]2− increases in place. It has been difficult to confirm the formation of cobalt carbonyls as Co2(CO)8 and HCo(CO)4during the course of the reaction, because their absortions overlap with those of the strong electronic charge transfer of tetrahedral iodocobalt(II) complex ions. From the experimental results and subsequent considerations, it has been shown that, when a comparatively large number of iodide ions are present in the solution, most of the cobalt (II) ions do not form cobalt carbonyls, but tetrahedral cobalt (II) complex ions of the [Co(AcO)4−nIn]2− type (n=1–4) during the course of the reaction, and that the reaction is accompanied by an increase in the number of tetrahedral iodocobalt(II) complex ions.
The Photolysis of Ethyl Chloroformate in Hydrocarbons
Authors: Pac Chyongjin , Tsutsumi Shigeru
Published: July 2006

The photolysis of ECF in cyclohexane, cyclohexene, oct-1-ene, and benzene has been carried out. It has been concluded that carbon-chlorine bond breaking has occurred to give ethoxycarbonyl radicals in a selective manner. The reactions of the radical in hydrocarbons have been qualitatively discussed, and it has been suggested that the radical had a life long enough to associate with a cyclohexyl radical in a solvent cage, but not a life long enough to dimerize and be added to carbon-carbon double bonds with less decomposition. Thus, cyclohexane, cyclohexene, oct-1-ene, and benzene were carboxylated. No chain reactions were observed in light- and dibenzoyl peroxide-induced reactions of ECF in hydrocarbons ; i. e., ECF was unreactive to alkyl radicals and radicals bearing an ethoxycarbonyl group on their α-carbon. The photolysis of ECF supplies a convenient method for the generation of ethoxycarbonyl radicals.
The Copolymerization of the Vinyl Monomer with a Cyclic Compound. I. The Cationic Copolymerization of Some Vinyl Monomers with 3,3-Bis (chloromethyl) oxetane
Authors: Aoki Shuzo , Harita Yoshiyuki , Otsu Takayuki , Imoto Minoru
Published: July 2006

The copolymerization of several vinyl monomers, such as styrene, α-methylstyrene and isobutyl vinyl ether, with 3,3-bis(chloromethyl)oxetane catalyzed by Lewis acids (boron trifluoride-diethyl etherate, stannic chloride and triethylaluminum-water) in methylene chloride at 0°C has been investigated. In these copolymerizations, the copolymers were not obtained, though a mixture of the corresponding homopolymers was obtained in some cases. The results have been explained on the basis of the differences in reactivity resulting from the structures of the two propagating chain ends.
A Geochemical Study of Selenium in Volcanic Exhalation and Sulfur Deposits. II. On the Behavior of Selenium and Sulfur in Volcanic Exhalation and Sulfur Deposits
Authors: Suzuoki Tetsuro
Published: July 2006

With regard to the temperature dependency of the sulfur/selenium ratio in volcanic gases, the factors which control the behavior of selenium and sulfur have been considered from the viewpoints of the chemical equilibrium, the vapor pressure and the thermal balance.

It has been found, from the examination of the equilibrium constants, that, unlike the case with sulfur, the most probable form of selenium in volcanic gases is free selenium. The effect of the vapor pressuse is significant in controlling the transfer of selenium and sulfur into volcanic gases. The results of the calculation of the thermal balance show that the observed wide variation in selenium concentration is due to the addition of water vapor.

On the other hand, it has been found that selenium and sulfur are extremely unsaturated at higher temperatures. This lack of saturation is caused by the dynamical processes of the introduction of these gases into volcanic gases.
Studies of the Liquid-Liquid Partition Systems. III. The Solvent Extraction of Americium(III) and Europium(III) Thiocyanate Complexes with Tributylphosphate
Authors: Sekine Tatsuya
Published: July 2006

The two-phase distribution of americium(III) and europium (III) has been studied between the hexane solution of tributylphosphate (TBP) and the aqueous solution of sodium thiocyanate at 25°C. From the distribution data when the organic phase was 5% (by volume) TBP in hexane and the aqueous phase was 5 m Na(SCN, ClO4), the following equilibrium constants have been obtained by a least-squares method:

(Remark: Graphics omitted.)

A remarkable salting-out effect has been observed when sodium perchlorate is added to the aqueous phase. This salting-out effect has been discussed, as has the solvation number of TBP in the adduct complexes in the organic phase.
The Preparation of Iminosulfonic Acid Derivatives by Means of Sulfinamides and N-Bromosuccinimide
Authors: Takei Hisashi , Watanabe Itaru , Mukaiyama Teruaki
Published: July 2006

It has been found that N-substituted benzenesulfinamides (I) react with thionyl chloride to give benzenesulfinyl chloride and the corresponding N-sulfinylamines, and that they are oxidized by treatment with bromine in an alkaline solution to give N-substituted sulfonamides.

When these benzenesulfinamides are treated with bromine or N-bromosuccinimide (NBS) in the presence of various primary or secondary amines, the corresponding benzeneiminosulfonamides are obtained in high yields. Similarly, the reaction of I, NBS and sodium p-nitrophenolate or sodium benzoate yields p-nitrophenyl benzeneiminosulfonate or N-benzoylbenzensulfonamide. These reactions are considered to proceed through the benzeneiminosulfonyl bromides formed by the oxidation of sulfinamides with bromine or NBS.
An Electron Paramagnetic Resonance and Spectrophotometric Study of Titanium(III)-Chelate Compounds with Nitrilotricarboxylic Acid and Its Derivatives
Authors: Codell Maurice , Fujiwara Shizuo , Nagashima Kozo , Seki Tokuko
Published: July 2006

Complexes formed by titanium(III) and agents which are similar in structure but varying in numbers of carboxyl groups have been studied by EPR and spectrophotometry. Among the reagents investigated, NTA, which posesses four coordinating groups, gives the largest EPR signals with a well-developed hyperfine structure. BHEG, which possesses two coordinating groups, gives much smaller signals, and even at the highest sensitivity setting of the instrument, no definite hyperfine structure can be detected. HEID, which posesses three coordinating groups, gives signals with two peaks, which indicates the simultaneous existance of two complexes in the solution. The ratios of the complexes of titanium(III) and NTA and HEID which exist in solution at various pH values have been spectrophotometrically determined.
The Structure and Properties of Supported Cobalt Catalysts
Authors: Hagihara Hiroshi , Echigoya Etsuro
Published: July 2006

1) The chemical states of cobalt in the supported catalysts may be classified into two types. One is the type in which the cobalt is not combined with the carrier but remains free on its surface. In the other type, cobalt oxide forms a complex with the carrier and resists reduction by hydrogen.

2) The ratio of the amounts of the two types varied both with the kind of carrier and with the method of preparation used.

3) The hydrothermally-formed cobalt-alumina and cobalt-silica catalysts form CoAl2O4 and cobalt hydrosilicate compounds respectively.

4) The course of the reduction of cobalt oxide in the catalyst is as follows: In the temperature range from 200 to 300°C, the cobalt(II, III) oxide is mainly reduced to cobalt(II) oxide, and later cobalt(II) oxide is reduced to β-Co between 300 and 500°C. The reduction temperature of cobalt(II, III) oxide is different for the various types of catalysts.

5) The catalyst which consists of a complex between the metal and its carrier-oxide is less active than the free metal catalyst for the hydrogena-tion reaction, and it is almost completely inactive in the hydrogenolysis reaction.

6) The results of the various analyses of the supported cobalt catalysts are in good agreement with one other.
Absorptinon Spectra of Dyes. VIII. The Correlation between Thermodynamic Quantities and Chemical Structure in Complex Formation
Authors: Tanizaki Yoshié , Hoshi Toshihiko , Ando Noboru
Published: July 2006

1) Using five kinds of dyes of Sky Blue FF and of similar structures, the equilibrium constants for a 1 : 1 and a 1 : 2 complex formed with Chrysophenine G have been determined by means of spectroscopy in the intervals of 20–60°C.

2) A new method of calculating the equilibrium constant has been proposed.

3) The free energy change (−ΔF), the enthalpy change (−ΔH) and the entropy change (−ΔS) for the complex formation have been obtained.

4) The correlation between these quantities and the chemical structure has been discussed and the following facts clarified: The larger the number of effective auxochromes (NH2, OH), the greater –ΔH and −ΔS become. The sulfonic group contributes to −ΔS through the location of that group. The dye molecule in the complex state is more planar than in the free state.
The Rotatory Dispersion and Stereochemistry of Organic Compounds. VII. Monosulfides and Disulfides Derived from Glucose and Glucosamine
Authors: Tsuzuki Yojiro , Tanabe Koko , Akagi Masuo , Tejima Setsuzo
Published: July 2006

Measurements have been made of the rotatory dispersions (265 to 700 mμ) and ultraviolet absorptions (225 to 340 mμ of various thiosugars, namely, there monothiodisaccharides (I, II, V), two dithio disaccharides (III, VI), and thiolevoglucosan (IV), in order to investigate the effect of sulfur atoms on optical activity.

The monosulfides, I, II and V, exhibit no absorption maxima and plain, negative RD curves. The disulfides, III and VI, exhibit absorption maxima at 235 to 250 mμ. Their negative RD curves are, accordingly, very steep, approaching the first extremes of the possible Cotton effect.

Thiolevoglucosan (IV), containing a “ heterocyclic ” sulfur atom, shows more bathochromic shifts than simple sulfides, and a stronger optical activity than levoglucosan. The strong rotatory contribution of the sulfur atom is also observed in acetylated thiotrehalose (V).

In thiosugars the acetamido group also shows a smaller rotatory contribution than the aceto-xyl group.

The dispersion data have been analyzed by means of the Drude equation, and the physical significance of the dispersion constants has been discussed.
The Reaction of Methyl Vinyl Ketone with Alkyl Grignard Reagents
Authors: Kurihara Yoshie , Higa Tatsuo , Sato Kikumasa , Abe Shigehiro
Published: July 2006

The reactions of methyl vinyl ketone with isobutylmagnesium bromide and ethylmagnesium bromide have been studied. Methyl vinyl ketone reacts with isobutylmagnesium bromide to give methylheptanone and 3-iso-amyl-2-vinyl-2-pentanol-4-one as a result of 1,4-addition; the latter compound is formed from 2 mol. of ketone and one mole of the Grignard reagent. On the other hand, in the reaction of ethylmagnesium bromide with methyl vinyl ketone, both 1,2- and 1,4-addition take place, and 3-methyl-1-penten-3-ol and 3-propyl-2-vinyl-2-pentanol-4-one are obtained. These keto-alcohols have been decomposed to the corresponding ketones and methyl vinyl ketone by heating or by treatment with sulfuric acid.
The Electrical Conduction of Iodine Complexes of Aromatic Diamines
Authors: Kusakawa Hideaki , Nishizaki Shun-ichiro
Published: July 2006

The magnitudes and temperature dependence of the electrical resistivities of aromatic diamine - iodine complexes have been studied on four aromatic diamines; 1,5-naphthylenediamine (NDA), benzidine (BEN), o-tolidine (TOL) and p, p′-diaminodiphenylmethane (APM).

As the donor is a non-conjugated molecule, the electrical conductivity of its iodine complex is inferior to that of the conjugated diamine.

BEN and TOL, which are polyphenylenediamines, are better electron donors for iodine than NDA, a diaminopolyacene; the characteristics of the electron donor for iodine of NDA are as strong as those of p-PDA.

The resistivity shows a minimum value at an iodine mole ratio above 1.0 in the cases of the conjugated aromatic diamine which involve two benzene rings. These iodine contents are higher than the corresponding value p-PDA-iodine, 0.8.
Corundum α-Al2O3 Formation from the Dehydration of Boehmite γ-AlOOH under Hydrothermal Conditions. II. The Reaction Rates and the Mechanism
Authors: Yamaguchi Goro , Yanagida Hiroaki , Fujimaru Takeshi
Published: July 2006

The authors have measured the reaction rates of corundum formation from boehmite under some hydrothermal conditions for the purpose of discussing the reaction mechanism. They have proposed that, in such cases as the crystallization of corundum or boehmite, there exists the hydrated poly ion of the structure intimately related to the lattice of the product phase and that the formation process often becomes the rate-determinant if no seed crystals of the product phase have been added beforehand. The seed crystal supplies the poly ions which accelerate the simple ions to transform themselves into the poly ions. The mechanism has been illustrated schematically and discussed in detail.
The Electrokinetic Potential of Lead(II) Sulfate
Authors: Morimoto Tetsuo , Hirata Yutaka , Kittaka Shigeharu
Published: July 2006

The ζ-potential of lead sulfate has been studied by applying the streaming potential method to samples obtained by various preparative methods and subjected to various temperature treatments. All the ζ-potentials measured have a positive sign, irrespective of such conditions as the kind of reagents and excess ions used in the preparation or the pH value of the reacating solution. It has been postulated that the surface of lead sulfate is hydrolysed to produce lead hydroxide, whose ζ-potential is explicit in the measurement of the streaming potential of lead sulfate. This is supported by the pH value of the saturated solution of lead sulfate. The surface behavior of lead sulfate in relation to the dye adsorption can also be explained in this way.
The Spectrophotometric Determination of Gallium(III) with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

The reaction between gallium (III) and xylenol orange has been studied spectrophotometrically in order to establish the optimum conditions for determining traces of gallium. Depending on the pH value of a solution, gallium (III) reacts with xylenol orange to form two complexes. The 1 to 1 complex which gives a maximum absorbance in the pH range from 1.2 to 1.7 has an absorption maximum at 530 mμ when measured against a reagent blank. The 1 to 2 complex which gives the maximum absorbance in the pH range from 4.5 to 5.5 has an absorption maximum at 502 mμ. Either with 1 to 1 and 1 to 2 complexes, Beer’s law is obeyed up to 60 mμ. of gallium. The apparent molar extinction coefficients of the 1 to 1 and the 1 to 2 complexes have been calculated to be 22900 and 16300 respectively. The present method is comparable in sensitivity with the stilbazo or the luminogallion IREA method. The addition of a small amount of fluoride is effective in eliminating some interfering cations, including aluminum (III), thorium(IV) and zirconium(IV).
The Electrooxidation of Absolute Methanol
Authors: Sasaki Kazuo , Nagaura Shigeo
Published: July 2006

From the several experiments described above, it can be concluded that the electroactive species in the anodic reaction of methanol in the moderate potential range is the methylate anion only.

The evidence for this conclusion will be summarized below.

The static potential of the platinized platinum electrode in absolute methanol is affected by the methylate concentration.

It is confirmed that a definite transition time in an anodic chronopotentiogram is observed only for the case of the methylate ion. The results from the potentiostatic experiments also support this conclusion.

Although this is the case, methanol is still electrolyzed to form formaldehyde at a higher potential range. Product analysis shows that the yield of formaldehyde is affected appreciably by the kind of supporting electrolyte. Except fluorine, an appreciable number of free halogen molecules is detected in the solution after electrolysis. Even in the case of an iodine/iodide couple, the thermodynamic potential is far more positive than that of methanol. It may be understood from this fact that the electrooxidation of neutral methanol is strongly irreversible. Furthermore, it seems quite plausible that some part of the methanol is decomposed by the attack of the free radicals (or atoms) formed by the discharge of salt anion. The reaction scheme can be formulated as follows:

X− → X+e

X+CH3OH → HX+CH3O (or CH2OH)

2CH3O (or CH2OH) → CH3OH+HCHO

Coinciding with this hypothesis, the current efficiencies of formaldehyde formation are increased in the order of the hydrogen-abstracting power of the four halogen atoms examined, i.e.,I<Br<Cl<F (see Fig. 9).

The mechanism of the electrolytic oxidation of methanol in aqueous solution has been studied by many authors, but no mechanism has yet been accepted without any ambiguity. The static electrode potential observed in an aqueous methanol solution rests near the thermodynamic redox couple:

CH3OH=HCHO+2H++2e 0.23 V . NHE

It is evident, however, that the real process does not proceed through such a simple reversible path.

Another mechanism proposed is the catalytic dehydrogenation:

CH3OH=HCHO+2H(Ads)

2H(Ads) → 2H++2e

This mechanism seems somewhat plausible, and some indirect evidence for it has been pointed out by the present authors.12)

Although it is difficult to state a definite conclusion about the reaction mechanism in the aqueous solution, the present conclusion, emphasizing the importance of the methylate ion, seems applicable in the case of the aqueous phase reaction. The fact that the performance of the methanol fuel cell in the alkaline medium is superior to that in the acidic one can thus be understood if the following reaction is taken into account:

CH3OH+OH−=CH3O−+H2O
The Rotatory Dispersion of Cobalt(III) Ammine Complexes Containing Amino Acid as a Unidentate Ligand
Authors: Fujita Junnosuke , Yasui Takaji , Shimura Yoichi
Published: July 2006

Fifteen new cobalt(III) ammine complexes containing amino acids as unidentate ligands have been prepared. The infrared, visible and ultraviolet absorption spectra of these complexes indicate that the oxygen of the carboxyl group acts as a donor atom. The circular dichroism and the rotatory dispersion of the unidentate complexes of the optically active α-amino acids and such chelate amino acid complexes as [Co(l-α-ala) (NH3)4]2+ have been measured. The results suggest that the magnitude of the anomalous dispersion of the α-amino acid complex in the region of its first absorption band seems to depend mainly on the conformational mobility of the optically active ligand in the coordination sphere.
The Separation of Rare Earths by Paper Electromigration and Focusing Chromatography
Authors: Kiso Yoshiyuki , Yamada Itsuko , Yamamoto Yuroku , Shinagawa Mutsuaki
Published: July 2006

The optimum pH value and concentration of EDTA for separating rare earths (lanthanum, cerium, praseodymium, neodymium, samarium and yttrium) by the technique of paper electromigration have been evaluated on the basis of the migration theory. The validity of the theory has then been justified experimentally. The best condition for separating was at the range of pH 1.7–2.1 of 5×10−3  m EDTA. Also, the applicability for focusing chromatographic separation has been examined with several pH arrangements between hydrochloric acid on the anodic side and a EDTA complexing agent solution on the cathodic side. Summarizing the above results, it has been concluded that the initial optimum pH of an anodic solution for separation may be obtained by selecting the pH range close to the expected one for the ordinary electromigration, while the effect of pH in a cathodic solution was not as severe as the former.
Effect of Density in the Radiolysis of n-Butane
Authors: Miyazaki Tetsuo , Shida Shoji
Published: July 2006

A study has been made of the effect of density on the radiolysis of n-butane at 170°C over the density region 0.006–0.575 g. cc−1. While G(H2) and G(C2H6) are not affected by the density change, G(CH4) and G(C3H8) decrease sharply in the density region from 0 to 0.1 g. cc−1. The latter facts may be interpreted in terms of the collisional deactivation of the excited ion. The rate constant of the fragmentation of the butane ion has been estimated from the deactivation-fragmentation competition scheme and compared with the rate constant calculated from the quasi-equilibrium theory. Agreement is satisfactory. The formation of methane by ionic fragmentation near the critical state has also been considered.
The Nitration and Sulfonation of 2,4,6-Triphenyl-1,3,5-triazine
Authors: Ogata Yoshiro , Izawa Yasuji , Kawashima Yuji
Published: July 2006

The nitration of cyaphenine (2,4,6-triphenyl-1,3,5-triazine) with a mixture of nitric and sulfuric acids has been found to give products with mostly meta- and partly para-substituted benzene rings. The composition of products varies with the varying reaction conditions. m,m′-Dinitrocyaphenine is the product of the highest number of nitro groups. The sulfonation of cyaphenine with oleum gives trisulfonated cyaphenine at meta-positions of benzene rings; it suffers desulfonation when left standing in the reaction mixture for a long time.
The Radiolysis of Mono-, Di- and Trimethylamine in the Gas Phase
Authors: Takamuku Setsuo , Sakurai Hiroshi
Published: July 2006

The γ-radiolysis of methylamines in the gas phase has been investigated, applying the absolute dosimetry involving the measurement of saturation ion currents in the gases during irradiation. The major volatile products are hydrogen, methane and ammonia. Ion-pair yields of hydrogen for mono-, di- and trimethylamine are 3.10, 2.78 and 1.78 respectively. Those of methane are 0.10, 0.45 and 0.41 respectively. The yields of hydrogen and methane are independent of the pressure up to 300 mmHg, but at pressures less than 100 mmHg there are slight decreases in hydrogen yields. The rate of hydrogen formation from methylamine is proportional to the radiation intensity, and the yield decreases in the presence of a small amount of ethylene. By kinetic analyses of the results with an added scavenger, it has been observed that 81% of the hydrogen formed from methylamine is caused by a radical process, while the value is 41% for trimethylamine.
The Ionization Constants of Organic Compounds. I. The Microscopic Ionization Constants of Tyrosine and Related Compounds
Authors: Yamazaki Futaba , Fujiki Kiyoko , Murata Yasue
Published: July 2006

A method has been formulated for the estimation of the microscopic ionization constants from spectroscopic data which measure the fractional ionization of one of the groups as a function of the pH value. This method has been applied at the ionic strength of 0.05 to the ionization of tyrosine (I), tyramine (II), 3-iodotyrosine (III), tyrosine methyl ester (IV), tyrosine ethyl ester (V), 3,5-diiodotyrosine (VI), and 3,5-dibromotyrosine (VII). The microscopic constants obtained are 9.55, 9.57, 10.08, 10.06 for I; 9.70, 10.09, 10.72, and 10.33 for II; 8.00, 8.70, 9.52 and 8.82 for III; 8.41, 7.27, 8.99 and 10.13 for IV, and 8.43, 7.31, 8.97 and 10.09 for V, in the order of pka, pkb, pkc, and pkd. For VI and VII, the pka values are 6.44 and 6.29, and the pkb values are 9.36 and 9.22, respectively. It has been illustrated that the method may be applied even in cases where ka<<kb. This approach can probably be extended to other Systems containing two dissociable protons, one of which affects the ultraviolet absorption and the other does not.