bluuebunny/crossref_metadata_2025_split huggingface dataset:
Measurement of Negative Ions Formed by Electron Impact. IV. Negative Ion Mass Spectra and Ionization Efficiency Curves of Negative Ions of m/e 17 and 16 from n-Propyl and Isopropyl Alcohols
Authors: Tsuda Satoru , Yokohata Akira , Kawai Michihiro 
Published: July 2006

Abstract
The negative ion mass spectra of n- and iso-propyl alcohols, with emphasis on their relative yields to the positive ions under 80 eV, 40 eV and 15 eV electron energies, and the ionization efficiency (IE) curves of OH− and O− ions to the extent of 50 eV electron energies were measured. In both cases, the electron impacts of 80 eV and 40 eV gave almost the same negative ion mass spectra, in which the relatively strong peaks of m⁄e 16 (O−), m⁄e 17 (OH−) and m⁄e 25 (C2H−) ions except for the decrement of C2H− ions in 40 eV for isopropyl alcohol were characteristic. For n-propyl alcohol, the ratio of the yield of CH2OH+ ions to that of O− ions (CH2OH+/O−) gave the values of 6.9×104 and 1.9×105 in 80 eV and 40 eV. For isopropyl alcohol the values of C2H4OH+/OH− were 3.3×104 and 6.4×104 in 80 eV and 40 eV, respectively. The comparison of the yield of negative ion in 10 eV with that of positive ion in 15 eV gave CH2OH+/O−=2.0×104 and C2H4OH+/OH−=2.3×103. Each appearance potential observed in IE curves is well interpreted by the following reactions. [OH− ions], for the first process C3H7OH(n- or iso-)+ e−→OH−+ C2H4+CH2+H, for the second process C3H7OH(n- or iso-)+ e−→OH−+CH3+CH2+CH2++e− or OH−+C2H4+CH2+H+e−. [O− ions], for the first process C3H7OH(n- or iso-)+e−→O−+C2H5+CH3, for the second process C3H7OH(n- or iso-)+e−→O−+C2H4+CH3+H or O−+C2H3+CH3+H2 and for the third process C3H7OH(n- or iso-)+ e−→O−+C3H7(n-or iso)+H++e− or O−+C3H5+H2+H++e−.
Reactions of Thiamine Disulfide Monosulfoxides with Mercaptans
Authors: Tsukamoto Goro , Watanabe Toshio , Utsumi Isamu 
Published: July 2006

Abstract
It was found that the reaction of thiamine disulfide monosulfoxide (I) with mercaptan is a competitive reaction between the so-called mercaptan-thiolsulfinate reaction and the apparent oxidation reduction reaction. This reaction offers an excellent method for the preparation of the mixed disulfides of thiamine and t-mercaptan or the unstable mixed disulfides, such as thiamineglutathione disulfides.
Alkoxysilanes. III. Preparation of Alkoxysiloxyaminosilane and Some of Its Reactions
Authors: Abe Yoshimoto , Kijima Ichiro 
Published: July 2006

Abstract
Bis(tri-t-butoxysiloxy)diaminosilane was prepared by the reaction of the corresponding di-chlorosilane with ammonia. It was also obtained by the reaction of silicon tetrachloride with tri-t-butoxysilanol in the presence of pyridine as a dehydrochloric acid agent, followed by the subsequent reaction of the mixture with ammonia. The alcoholysis, transamination reaction, hydrolysis, and acetolysis of this compound with n-butyl alcohol, phenol, aniline, n-butylamine, water, and acetic acid led to the formation of the corresponding bis(tri-t-butoxysiloxy)silane derivatives. In these reactions, the measurement of the ammonia evolved made it possible examine the relative reactivity of the reactants. An attempt to isolate the triaminosilane by the reaction of tri-t-butoxysiloxytri-chlorosilane with ammonia resulted in the formation of tetraaminocyclotetrasilazane and a polymeric substance containing the silicon-nitrogen bond.
Kinetic Features of the Redox-polymerization of Acrolein with the Potassium Persulfate-Silver Nitrate System
Authors: Kagiya Tsutomu , Morita Shigeru , Fukui Kenichi 
Published: July 2006

Abstract
The polymerization of acrolein initiated by the potassium persulfate-silver nitrate redox system in water was studied at 0°C from the point of view of kinetics. The potassium persulfate concentration was varied over the range from 15.75 to 157.5 mmol/l, and that of the initial monomer, from 0.462 to 2.675 mol/l, while the concentration of silver nitrate was 31.5 mmol/l. Both the polymerization rate and the molecular weight of the polymer were found to increase with the reaction time in the early stage, while in the stage of higher conversion the polymerization rate was gradually reduced and the molecular weight remained constant. In the early stage of the polymerization, the polymer yield showed a first-order dependence on the potassium persulfate and initial monomer concentrations. The molecular weight of the polymer was proportional to the monomer concentration, independent of the catalyst concentration. From these results, the kinetic features were discussed.
Graphical Evaluation of the Rate Constants of the Elementary Reactions in the Acrolein Polymerization with the Potassium Persulfate-Silver Nitrate Redox System
Authors: Kagiya Tsutomu , Morita Shigeru , Fukui Kenichi 
Published: July 2006

Abstract
A quantitative study was made of the redox-polymerization of acrolein initiated by the potassium persulfate-silver nitrate system. The reaction mechanism of this polymerization was proposed on the basis of the results of the time-conversion, time-molecular weight curves, and also on the basis of the characteristic features of this polymerization, reported in a previous paper. The rate constants of the elementary reactions in this polymerization were estimated by a graphical method. In the early stage, neither the termination nor the transfer reaction is very remarkable as the initiation reaction, but in the later stage the termination reaction by a recombination of the polymer radical and the transfer reaction increase with the reaction time, as does the initiation reaction also.
Catalytic Activities of Salicylaldehyde Derivatives. I. Catalytic Effects of 4-Formyl-3-hydroxyphenyltrimethylammonium Bromide on the Racemization of l-Amino Acid
Authors: Ando Makoto , Emoto Sakae 
Published: July 2006

Abstract
The pyridoxal-like catalytic effects of salicylaldehyde derivatives on the racemization of amino acid in the presence of a metal ion is known to be promoted by the substitution of an electron-attracting group in the benzene ring. Of the salicylaldehyde derivatives tested thus far, 4-formyl-3-hydroxyphenyltrimethylammonium bromide shows the most effective catalytic activity of racemization at pH 10 and at 80°C; the rate constant was 11.0×10−3 min−1. The catalytic activity of this compound was studied under various conditions; the activation energy of the racemization of l-glutamic acid at pH 10 was 14.3 kcal/mol.
Catalytic Activities of Salicylaldehyde Derivatives. II. Kinetic Studies of the Racemization of Amino Acid
Authors: Ando Makoto , Emoto Sakae 
Published: July 2006

Abstract
In the racemization reaction of l-glutamic acid, catalyzed by salicylaldehyde derivatives and cupric ions, the rate constants, k, of 3-bromo-, 3-methoxy-, 3-methyl-, 3-nitro-, 4-methyl-, 5-bromo-, 5-methoxy-, 5-methyl-, and 5-nitro-salicylaldehydes and of salicylaldehyde were measured and the kinetic relation between the rate constant, k, of the salicylaldehyde derivatives and the corresponding Hammetfs constant, σ, was studied. A linear relation between logk and the σ of 4- or 5-substituted salicylaldehydes and another linear relation between logk and the σ of 3-substituted salicylaldehydes were found. The activation energies of the racemizations catalyzed by pyridoxal, 3-nitro-, and 5-nitro-salicylaldehydes and by salicylaldehyde were determined, but no distinct difference between 3-nitrosalicylaldehyde and 5-nitrosalicylaldehyde was observed.
Conformational Studies of Acetonated α-l-Sorbo- and β-d-Fructopyranoses by Means of Proton Magnetic Resonance Spectroscopy
Authors: Maeda Takashi , Tori Kazuo , Satoh Shiroh , Tokuyama Kanji 
Published: July 2006

Abstract
The favored conformations of the pyranose rings of several acetonated α-l-sorbo- and β-d-fructopyranoses have been revealed by proton magnetic resonance spectroscopy. The conformations of the rings of the pyranoses are unchanged by the introduction of 1,2-O- or 1,3-O-isopropylidene groups in α-orientation of l-sorbose, but they are affected by the introduction of the 2,3-O-isopropylidene group. These findings support the fact that 2,3-O-isopropylidene-α-l-sorbopyranose was not obtained by the acetonation of l-sorbose. The rings of diacetonated d-fructopyranoses with a cis-fused acetal ring adopt a distorted conformation; however, those of diacetonated l-sorbopyranoses with a trans-fused acetal ring are only slightly distorted from the stable 1C conformation. Angyal’s anticipation of the difficult acetalation of the trans-glycol of a pyranose has been further experimentally supported.
The Acetalation Mechanism of l-Sorbose
Authors: Maeda Takashi , Miichi Yoshiyuki , Tokuyama Kanji 
Published: July 2006

Abstract
The following reaction mechanism of the acetonation of l-sorbose is proposed:
(Remark: Graphics omitted.)
2,3:4,6-di-O-acetal (furanose) (II). The pyranose-to-furanose ring conversion (I→II) proceeds via the keto-form intermediates Vk and VIk; VIk is formed by the preferable attack of acetonating reagents on the primary hydroxyl group at the C6 of Vk followed by cyclization with the hydroxyl group at C4. The isolation of such keto-form intermediates as were successfully obtained from the acetalations of 1-O-methyl- (X) and 1,6-di-O-methyl-l-sorboses (XVIII) gave strong support to the above mechanism. This acetonation mechanism can also be used in the other acetalations of I; however, in the case of the benzylidenation there is a possibility that the reaction might be via the pathway of 1,3-O-acetal (pyranose)\ightleftarrows1,3-O-acetal (furanose) (Vb)→1,3: 4,6-di-O-acetal (furanose).
A Destructive Ethylation Reaction of Benzene with 3-Methylpentane-1-14C
Authors: Sugahara Yukio , Hayami Jun-ichi , Sera Akira , Goto Ryozo 
Published: July 2006

Abstract
The destructive alkylation reaction of benzene with 3-methylpentane to give ethylbenzene in the presence of aluminum chloride was investigated. When 3-methylpentane-1-14C was employed, radioactive ethylbenzene was obtained. A radioassay of radioactive ethylbenzene showed that: a) the specific radioactivity of the ethylbenzene was about one-third that of the starting 3-methylpentane-1-14C, and b) more than 90% of the radioactivity of the ethylbenzene was present on the β-carbon atom of the ethyl group. These findings suggested a preceding equilibrium between 3-methylpentane and 2-methylpentane, which resulted in an equivalent localization of the radioactive label on three methyl groups of these C6-hydrocarbons. A carbonium-ion mechanism including an intermediate ethyl cation was discussed in detail.
Synthesis of 2-Amino-4-hydroxy-6-acetyl-7-methyl-7,8-dihydropteridine
Authors: Sugiura Katsura , Goto Miki 
Published: July 2006

Abstract
2-Amino-4-hydroxy-6-acetyl-7-methylpteridine was synthesized by condensation of 2,4,5-triamino-6-hydroxypyrimidine and triketopentane. Reduction of this compound with sodium amalgam yielded a coloring matter, whose UV-spectra and chemical reactions strictly correspond to those of sepiapterin or isosepiapterin. On the basis of NMR spectra, the coloring matter was proved to be 7,8-dihydro-2-amino-4-hydroxy-6-acetyl-7-methylpteridine. Hence, it can be concluded that sepiapterin has the 7,8-dihydro structure as proposed by Nawa.
Partial Asymmetric Synthesis in the Simmons-Smith Reaction. III. A Modification of the Reaction
Authors: Sawada Seiji , Inouye Yuzo 
Published: July 2006

Abstract
A modification of the Simmons-Smith reaction, which involves a prior reaction of ethyl iodide with zinc copper couple followed by addition of methylene iodide and oleflns, was proposed. The improved yields of cyclopropane products were obtained with various olefin substrates. It is likely that the operating species in the present modification is ethyliodomethylzinc.
The Rate of Penetration of Photographic Chemicals into Gelatin Layers. I. Diffusion Rate of Developing Materials
Authors: Iwano Haruhiko 
Published: July 2006

Abstract
The rate of diffusion of various kinds of developing materials through coated gelatin layers was determined by using silver halide as a detector. p-Phenylenediamines have the biggest diffusion constants among materials tested. They have no pH-dependency nor concentration-dependency. p-Aminophenols have slightly lower diffusion constants than the corresponding p-phenylenediamines. The constants increase with increase in molecular sizes and also with pH. Hydroquinones have relatively low diffusion constants. They are considerably affected by variation of pH, concentration and ionic strength. These characteristics are discussed in connection with the chemical structures of developing materials.
Hybridization of Carbon and Equilibrium Distance
Authors: Miyazaki Tomoo , Ohbayashi Hidehito 
Published: July 2006

Abstract
The CNDO/2 method, an approximate self-consistent molecular orbital theory, has been applied to the calculation of equilibrium distances of the carbon-hydrogen bond and the normal and hypothetical carbon-carbon single or double bonds which are usually considered te-te, tri-tri, di-di and te-tri single bonds or tri-tri and di-di double bonds between carbon hybrids. The electronic interaction energies between non-adjacent atomic orbitals for sigma system considering appropriate carbon hybrids have been estimated. From the results of these calculations, it follows that the carbon-carbon bond length of sigma system is little affected by the types of hydbridization of carbon atoms.
Studies of the Direct Dissolution of Metal in a β-Diketone Reagent
Authors: Sato Kimitaka , Kammori Ohiko 
Published: July 2006

Abstract
As it was found that metallic iron is dissolved in acetylacetone (Hacac), the interaction between the solute and the solvent in the dissolution phenomena, together with the process of the dissolution of metal, were examined in detail in order to apply it to analytical techniques. The factors of the oxygen, the co-existing water, and the dissociated proton in acetylacetone were shown to be effective in the dissolution. With typical β-diketones, the exception of acetylacetone, such as trifluoroacetylacetone (HTFA), hexafluoroacetylacetone (HHFA), benzoyltrifluoroacetone (HBTA), 2-furoyltrinuoroacetone (HFTA), and 2-thenoyltrifluoroacetone (HTTA), were also employed; they were shown to have the same properties as the above one. The relationship between the solubilities of metals and the effect of adding an organic solvent, the equilibrium reactions of fluorine-containing β-diketones with water or alcohols, or the preferred enol forms of trifluorosubstituted β-diketones, were also discussed, paying attention to the accelerating effects of the solvents on the dissolution.
Effects of Cation Vacancies of the Diffusion of Nickel Ions in Defective Spinels
Authors: Yamaguchi Goro , Nakano Mitsuko , Tosaki Mamoru 
Published: July 2006

Abstract
In order to clarify the influence of composition-dependent cation vacancies in defective spinels on the diffusion, the diffusion rates of Ni2+ in several kinds of defective spinels (MgO·xAl2O3, where x=1.1,1.2,1.3,1.4 and 1.5) and a perfect spinel (MgO·Al2O3) were measured by the use of an electron probe micro-analyzer, and the diffusion coefficients were obtained. The diffusion coefficients were found to be linear to the concentrations of the composition-dependent vacancies. The so-called activation energies which were calculated from the Arrhenius plot were about 70 kcal/mol for the defective spinels and 106 kcal/mol for the perfect spinel. It may be concluded that composition-dependent cation vacancies govern the diffusion of cations in the defective spinel, while temperature-dependent vacancies probably predominate in the perfect spinel.
The Chromium(III) Complexes with β-Aminoethylsulfonic-N,N-diacetic Acid and Aspartic-N,N-diacetic Acid
Authors: Uehara Akira , Kyuno Eishin , Tsuchiya Ryokichi 
Published: July 2006

Abstract
The following chromium (III) complexes with the β-aminoethylsulfonic-N,N-diacetic acid (AEDA) and aspartic-N,N-diacetic acid (ASDA) were newly prepared; K3[Cr(aeda)2]·4H2O (pale red) (I), [Cr(OH)(Haeda)(o-phen)]·2H2O (orange) (II) and [Cr(Hasda)(H2O)2]·H2O (reddish purple) (III). From the results of spectral measurments, it was found that AEDA acts as a quadridentate ligand as well as a terdentate one in an aqueous solution, but only as a terdentate ligand in a crystal state, and that the coordinating ability of the oxygen atom of sulfonic radical in AEDA is weaker than that of carboxylic radical in ammoniapropionicdiacetic acid (APDA). In Complex III, ASDA behaved as a quadridentate ligand rather than as a quinquedentate. Complexes II and III showed some interesting thermal decomposition processes. The former lost one mole of water at 110°C from the hydrogen atom in free sulfonic acid radical and the coordinated OH group, accompanied with the increase of coordination number of AEDA from 3 to 4. In the latter, one mole of crystalline water was lost first, and then the carboxylic acid bound to the methylene group at β-position in the ligand was decomposed to liberate carbon dioxide, and the coordinated asda was changed into apda.
The Kinetics of the Ligand-substitution Reactions of Nitrilo(diacetic)-propionato- and Nitrilo(diacetic)isopropionatoniccolate(II) Ions with EDTA, and of Taurin-N-diacetatoniccolate(II) Ions with EDTA and CyDTA
Authors: Kimura Masaru 
Published: July 2006

Abstract
The kinetics of the reactions of nickel(II)-nitrilo(diacetic)propionate (NDAP) and nickel(II)-nitrilo(diacetic)isopropionate (NDAIP) complexes with ethylenediaminetetraacetate (EDTA) ions, and those of the nickel (II)-taurin-N-diacetate (TDA) complex with EDTA and trans-1,2-cyclohexanediaminetetraacetate (CyDTA) ions, have been studied polarographically in solutions with pH 4.8–6.0 at 25°C and at an ionic strength of 0.2. All the reactions except those with CyDTA proceeded through four reaction paths, and the rate constants for the reaction paths were determined. The reaction of the nickel(II)-TDA complex with CyDTA was found to proceed only through the complete dissociation of the Ni(II)-TDA complex. There was not a direct reaction of the complex with CyDTA. Consequently, the overall reaction with CyDTA became much slower than that of the same complex with EDTA. The rate constants obtained were compared with those of the similar reactions of the nickel (II)-nitrilotriacetate (NTA) complex with EDTA and CyTDA which had been reported previously. The rate of the dissociation reaction of nickel(II) complexes increased in the order: NDAIP≤NDAP&lt;NTA&lt;TDA. Especially, the rate of the Ni(II)-TDA complex was about 30 times that of Ni(II)-NTA complex.
Shock Induced Reactions of Methane with Nitrous and Nitric Oxides
Authors: Drummond L J 
Published: July 2006

Abstract
Reflected shock waves, generated in a 5×3 inch shock tube, have been used to ignite mixtures of methane-nitrous oxide and methane-nitric oxide. Monochromators, a pressure transducer and an oscilloscope were used to determine the induction period to ignition (τ) after the reflected wave passed the window. A flash lamp and spectrograph were also used to obtain spectra before and after explosion. For CH4-N2O mixtures it was found that the plot of log(τ[N2O]p5) against inverse temperature was linear and the activation energy was about 60 kcal/mol. This indicates that the rate controlling process was the reaction N2O(+M)→N2+O(+M). However, the reaction CH3+N2O→CH2+N2+OH may also be important. The results for CH4-NO mixtures could be expressed by log(τ[NO]p5)=−10.2+49000⁄4.58T which suggests to the reaction CH2+NO→CH+HNO may be rate controlling. Spectrographic plates showed that CN and OH were present during the induction period but only OH was detected after explosion. This indicates that the reactions CH+NO→CN+OH and CN+NO→N2+CO may be a significant mechanism for achieving the reduction of nitric oxide.
Thermal Decomposion Reactions of Chromium(III) Complexes. Hexammine, Chloropentammine and cis-Dichlorotetrammine Complexes
Authors: Tanaka Nobuyuki , Nagase Kenzo 
Published: July 2006

Abstract
The thermal decomposition reactions of [Cr(NH3)6]Cl3, [CrCl(NH3)5]Cl2 and cis-[CrCl2-(NH3)4]Cl in solid state were studied by the manometric, infrared spectroscopic and reflectance spectroscopic methods. The decomposition of these complexes in vacuum was initiated by substitution of an outer-sphere chloride ion for a coordinated ammonia. The rate constants, activation energies and activation entropies of these substitution reactions were obtained and the possible reaction processes were discussed. The products cis,cis-[CrCl3(NH3)3] and cis,trans-[CrCl3(NH3)3] were obtained on the heating of cis-[CrCl2(NH3)4]Cl.
Reaction of Titanium Tetrahalides with Phenylhydrazones
Authors: Aggarwal R C , Singh S K 
Published: July 2006

Abstract
Titanium tetrafluoride reacts with benzaldehyde phenylhydrazone to yield 1:1 adduct and with benzophenone phenylhydrazone 1:2 as well as 2:1 adducts, while other tetrahalides form 1:1 adducts with both the phenylhydrazones. All these complexes are coloured and stable at room temperature. The infrared spectral studies of phenylhydrazones and their titanium (IV) complexes have been made in the 4000–200 cm−1 region.
Configuration of 1,3-Dipolar Cycloaddition Products of Nitrones with N-Phenylmaleimide
Authors: Iwakura Yoshio , Uno Keikichi , Hongu Tatsuhiko 
Published: July 2006

Abstract
1,3-Dipolar cycloaddition reaction of aldonitrones such as C-2-furyl-N-phenyl-, C,N-diphenyl-, and C-2-thienyl-N-phenylnitrone with N-phenylmaleimide was carried out. The product was separated into two stereo isomers, cis and trans isoxazolidines with respect to H3 and H4, which were identified by NMR spectra. Spin-spin coupling of protons on C3 and C4 of isoxazolidine ring was found to be 8.4–9.0 cps for cis isomers and to be zero for trans isomers.
Effect of Ultrasonic Waves on Eriochrome Black T
Authors: Prakash Sheo , Jain S K 
Published: July 2006

Abstract
Ultrasonic waves of high frequency (1 Mc/sec) have been employed to study the effects on the dilute aqueous solution of Eriochrome Black T. The deaeration of the solution by nitrogen does not greatly affect the rate of decolourization. The process is irreversible and the kinetic study shows it to be unimolecular. Oxidation and subsequent destruction of the dye molecule has been found to be the cause of the fading of the dye solution.
Alkaline Hydrolysis of Aryl Benzenethiolsulfinates
Authors: Oae Shigeru , Yoshikawa Yoichiro , Tagaki Waichiro 
Published: July 2006

Abstract
The alkaline hydrolysis of substituted phenyl benzenethiolsulfinates has been kinetically investigated. The rates were correlated with the second order kinetic equation, first order with respect to each of the hydroxide and the ester concentration. The second order rate constant for the unsubstituted ester was found to be 3.17×103 l/mol sec (water, 30°C). The Hammett ρ values were found to be ρX,Y=H=2.4 and ρY,X=H=1.6 for (Remark: Graphics omitted.) respectively.
Effect of Cationic Detergents on the Lecithin Stabilized O/W Emulsion
Authors: Sastry T G , Srivastava S N 
Published: July 2006

Abstract
An oil-in-water system (Nujol being the oil phase) stabilized by the phospholipid, lecithin, has been chosen in this study. The system being negatively charged initially, cationic detergents like lauryl pyridinium chloride (LPC), Cetyl pyridinium bromide (CPB), Phenyl trimethyl ammonium chloride (Ammonyx-200) and Cetyl dimethyl benzyl ammonium chloride (CDBAC) have been employed in order to study their influence on the flocculation and coalescence rates and the degree of aggregation haemocytometrically. Zeta potentials (ξ) have been determined at the corresponding concentrations of the detergents by microcataphoresis and with these values the potential energies and then ultimately the operating van der Waals constant of the system has been determined. From the log C-ξ values it is evident that except Ammonyx-200 which is not an effective cationic detergent, all the others have reversed the charge of the system and their efficiencies are in the order CDBAC&gt;CPB&gt;LPC. The different binding parameters, number of binding sites available for adsorption and free energy of the surface have also been calculated.