Showing papers in "Bulletin of the Chemical Society of Japan in 1959"

Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. I. Biphenyl

Abstract: 1) The ultraviolet absorption spectra of biphenyl in the crystalline state, in the solution state, and in the vapor state have been discussed in detail. 2) The relation between the position of conjugation band in the spectra of biphenyl and the spatial configuration of the molecule has been clarified by calculations based on the simple LCAO molecular orbital method. 3) By using the results of the calculations, it has been inferred from the analysis of the absorption spectra that the angles between the planes of the two benzene rings in the most probable conformations of biphenyl in the solution state and in the vapor state are about 20°C and about 40∼43°C, respectively. These values coincide fairly well with the values estimated by other workers on different grounds.

The Crystal Structure of Bis(adiponitrilo)copper(I) Nitrate

Abstract: The crystal structure of bis(adiponitrilo)-copper(I) nitrate has been determined by the two-dimensional Fourier method. It is orthorhombic Pnnn with two formula units in a cell of dimensions: a=9.41±0.02 A, b=13.73±0.02A and c=5.85±0.01 A.The crystal consists of infinite three-dimensional networks of complex ion [Cu(NC–CH2–CH2–CH2–CH2–CN)2]nn+ and nitrate ions. A copper atom is tetrahedrally surrounded by four nitrogen atoms at a distance of 1.98 A. Each adiponitrile molecule is coordinated to two different copper atoms with nitrogen atoms of both ends, forming a planar zigzag configuration of methylene groups. Thus the copper atoms and the ligand molecules form a complicated threedimensional 4-connected network. The nitrate ions lie perpendicularly to the a-axis. The trigonal nitrate ion seems to have statistical azimuthal orientations in the crystal and its apparent symmetry becomes 222.All the atoms in the group Cu–N–C–C lie approximately on a straight line. This fact and the observed carbon-nitrogen d...

Dissociation Constants of Some Carboxylic Acids in Mixed Aqueous Solvents

Abstract: Several authors determined dissociation constants of acids such as benzoic, succinic and azelaic acids in mixed solvents and reported that the dissociation constants determined in aqueous dioxane were higher than those determined in aqueous alcohols having the same dielectric constants. However, if the variation of the amount of water in mixed solvents is taken into consideration in calculating the dissociation constant, an acid has almost the same dissociation constant in various mixed solvents with the same dielectric constant.

Electron Diffraction Investigation on the Molecular Structure of n-Butane

Abstract: The molecular structure of n-butane has been investigated by means of the sector-microphotometer method of electron diffraction. The least-square analysis of the radial distribution curve has been carried out both for modified and unmodified curves giving the internuclear distances as well as their mean amplitudes and the bond angles. The estimation of experimental standard errors has been made by examining various sources of errors. Important results are the following: a) The average distance of the C–C bonds is 1.539±0.003A. b) The angle C–C–C is 112°9′± 9′, is considerably greater than the tetrahedral angle. c) The position of hydrogen atoms is located with considerable accuracy; C–H=1.100±0.003A and

Intramolecular Interaction between Hydroxyl Group and π-Electrons. IV. Rotational homers of Alcohols and Shift of νO–H Absorptions in Phenyl Substituted Alcohols

Abstract: The authors observed symmetric νO–H absorptions for methanol and tertiary alcohols and unsymmetric bands for primary and secondary alcohols. The unsymmetric band was divided into two bands, assuming that the band is an overlap of the two symmetric bands. The idea of the rotational isomerism was successfully introduced for assigning the band and the following points were concluded. 1) Types I and IV show absorption bands at 3644∼3636 cm−1, type II at 3626∼3629 cm−1, type III at 3615∼3618 cm−1, type V at 3616∼3619 cm−1, type VI at 3608∼3611 cm−1, and type VII at 3613∼3617 cm−1. 2) The exception is dialkylphenylcarbinols which show the νO–H absorptions at about 3620 cm−1 and 3608 cm−1, the former being assigned to type III and the latter to type VII. This ruling-out may be attributed to the steric effect and the rotation around the CPh–Cα axis. The steric effect on the integrated intensities and on the wave number where νO–H absorption falls is also discussed. The differences between types II and IV and betw...

Study on the Reductive Spinel—A New Spinel Formula AlN–Al2O3 instead of the Previous One Al3O4

Abstract: A compound between aluminum oxide and aluminum nitride can be produced in a reductive atmosphere above 1650°C. A new spinel formula AlN–Al2O3 should be adopted instead of the previous one Al2O–5Al2O3 or Al3O4. The physical constants of AlN-Al2O3 are as follows: crystal structure Fd3m, Z=8, a=7.940 A; density 3.78g./cc.; dielectric constant 23.8; refractive index 1.80; magnetic susceptibility −0.34×10−6/g

Estimation of the Energy of Hydrogen Bonds Formed in Crystals. I. Sublimation Pressures of Some Organic Molecular Crystals and the Additivity of Lattice Energy

Abstract: Sublimation pressures of a number of organic molecular crystals were measured by a viscosity gauge. The heats of sublimation of these compounds were examined in relation to their molecular structures, and it was concluded that an additivity rule could be applied to the lattice energies of these crystals as a first approximation.

Effects of Dry Grinding on Kaolin Minerals. I. Kaolinite

Abstract: The effects of several-hundred-hour mechanical-mortar dry grinding of kaolinite were studied by X-ray, thermal, electron microscopic and other methods. It has been found that there are two sorts of structural change in the process of dry grinding of kaolinite. One is the production of a non-crystalline substance attended by the disordering of the crystalline part, and the other is the reaggregation process. The process of the reduction in the particle size and the process of the production of the non-crystalline substance are connected to the process of the reaggregation. In a certain stage of the dry grinding, the reaggregates are spherical particles which have a zeolitic structure. As the grinding further progresses, the structure of the crystalline part in this radial particle becomes disordered due to the mechanical stress, and it changes into an amorphous substance at last. Consequently, the effect of dry grinding of kaolin mineral depends on the structural perfectness of alumino-silicate layers of t...

Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. II. o-Alkyl-and o,o′-Dialkylbiphenyls

Abstract: The method described in the preceding part of this series has been applied with allowance for the electronic bathochromic effect of the substituents to o-alkyl- and o,o′-dialkylbiphenyls, and the relation between the ultraviolet absorption spectra and the most probable spatial configurations of these compounds has been clarified, resulting in the conclusion that the interplanar angle in o-methylbiphenyl as well as its analogues is about 60°C and that o,o′-dimethylbiphenyl as well as its analogues has the cis-configuration in which the interplanar angle is about 70°C. On the basis of the result, the interpretation by Braude and Forbes of the spectra of o-methyl- and o,o′-dimethylbiphenyl has been criticized. In addition, the inferred spatial configurations of these biphenyl derivatives have been correlated with some physical and chemical properties of these and some related compounds.

The Preparation and Properties of N-Salicylideneglycinato-aquo-copper(II), Sodium N-Salicylideneglycylglycinato-cuprate(II) and Related Compounds

Abstract: The two new compounds, N-salicylideneglycinato-aquo-copper(II) and sodium N-salicylideneglycylglycinato - cuprate(II) were prepared and investigated as to their structure. Their infrared, visible and ultraviolet absorption spectra together with those of some related compounds were measured and discussed.

Vapor Pressure of Molecular Crystals. XIII. Vapor Pressure of α-Glycine Crystal. The Energy of Proton Transfer

Abstract: Sublimation pressures of crystalline α-glycine were measured between 138 and 153°C by the effusion method. The pressure equationlogP(mmHg)=13.666-(6816.8/T) fits well the experimental data. The heat, entropy and free energy (at 25°C) of sublimation were 31.18±0.49 kcal./mole, 49.33±1.17 cal./deg. mole and 16.47±0.60 kcal./mole, respectively. An energy cycle was constructed which correlates zwitterion and molecule in crystal and vapor states, and hydrated zwitterion and molecule in solutions. The observed heat of sublimation corresponds to the change in heat content in going from the zwitterioncrystal to gaseous molecules. The molecular configuration is more stable in vapor state. By using the experimental values of the heat of sublimation, the heat of solution of crystals into water and the temperature dependence of pKa in solution, with the help of the theoretical values of the lattice energy of the crystal, the following heat values were determined; the heat of proton jump in vapor, NH3+CH2COO− → NH2CH2...

Dichroism of Dyes in the Stretched PVA Sheet. II. The Relation between the Optical Density Ratio and the Stretch Ratio, and an Attempt to Analyse Relative Directions of Absorption Bands

Abstract: 1) An expression for the optical density ratio was derived as a function of the stretch ratio. 2) Dichroism of the crystal violet and auramine yellow ion in stretched PVA sheets was observed, and the relation of the optical density ratio to the stretch ratio was plotted. It was shown that the theoretical expression derived here could explain rather well the experimental relation between these two quantities. 3) The analytical results were as follows. The main absorption band and the shoulder of the crystal violet ion did not orginate from the two isomers but were perhaps due to one species. For the auramine yellow ion the angle between the transition directions corresponding to the first and the second band might be approximately a right angle provided that the absorption-planes were in a same plane.

Intramolecular Interaction between Hydroxyl Group and π-Electrons. VI. Electronic Effect on the Interaction in ω-Arylalkanols

Abstract: The electronic effect on the intramolecular interaction between the hydroxyl group and the π-electrons of the benzene nucleus was studied with various ω-aryl-alkanols. In 2-arylethanols, introduction of an electron-releasing group into the benzene nucleus gives rise to the shift of the νO–H absorption maxima to a lower wave number and to greater integrated intensities of the band due to the interacting form, and introduction of an electron-attracting group to a higher wave number and smaller integrated intensities. However, the wave number of the band due to the interacting form is not affected by the position of the substituent, as far as the substituent is the same. Thus, the structure represented by IX is favored. On the other hand, a compound with an electron-releasing group in the meta position always shows greater integrated intensities of the band due to the interacting form than the para-substituted isomer and this fact saves structure VIII from entire rejection. Hence, the authors tentatively ass...

Intramolecular Interaction between Hydroxyl Group and π-Eelctrons. V. Electronic Effect in Arylcarbinols and a Preliminary Note on the Interaction in Benzylaniline Derivatives

Abstract: Absorption due to the O–H stretching vibration in the fundamental region was measured with fourteen benzyl alcohol derivatives to see the electronic effect of the substituent on the interaction between the hydroxyl group and the π-electrons and the following conclusions are deduced. 1) The nature of the interaction or the structure of the molecule which gives rise to the νO–H absorption at 3617 cm−1 is discussed and the interaction between the hydroxyl group and the π-electron on the carbon atom to which hydroxymethyl group is attached (structure III) is favored. 2) The consistency of the wave numbers at which two νO–H absorptions appear, gives further support to the idea that these absorptions originate in the existence of the two rotational isomers. 3) (Remark: Graphics omitted.) is in linear relation with Hammett’s σ values and the σ value of the m-benzyloxyl group is estimated as −0.204. A similar phenomenon is also observed in the substituted benzylanilines.

Polymerization of Aminoacetonitrile

Abstract: Aminoacetonitrile sulfate was heated with kaolin and/or Japanese acid clay at 120∼140°C for 5 hr. The presence of glycyl-glycine and glycyl-diglycine in the extract and the partial hydrolysate of this reaction product was confirmed by paper and column chromatography.

The Crystal Structure of Bis(succinonitrilo)copper(I) Nitrate

Abstract: The crystal structure of bis(succinonitrilo) copper(I) nitrate has been determined by two dimensional Fourier method. It is monoclinic P2⁄a with two formula units in a cell of dimensions: a=11.62±0.03 A, b=5.31±0.01 A, c=9.53±0.03 A and β=98.8°±0.2°. The crystal consists of nitrate ions and polymeric chains of the following composition: (Remark: Graphics omitted.) These chains run parallel to the a-axis-A succinonitrile molecule takes a gauche form with respect to the central C2–C3 bond. A copper atom is surrounded tetrahedrally by four nitrogen atoms with Cu–N distances of 1.96 and 2.02 A. These facts are in close agreement with infrared spectral observations. All the atoms in the group Cu–N–C–C lie almost on a straight line. This fact and the observed C–N distance of 1.14 A suggest that the bond character in the C–N group may essentially be expressed as C≡N.

Studies on the Silk-Palladium Catalyst. I Preparation and Stability

Abstract: 1. The highest hydrogenation activity was obtained when the silk-palladium catalyst was prepared by boiling the silk fibroin fibers with 0.1% palladous chloride solution in 0.1 N acetic acid for 8 min. and then hydrogenating the resulting chelate. 2. The catalyst prepared as above was, however, devoid of the capacity of asymmetric catalysis, although the same catalyst prepared in distilled water (instead of dilute acetic acid) was able to achieve asymmetric reduction. 3. The catalyst and its precursor chelate could be stored in dry state without any loss of activity. 4. The synthetic fiber, 6-Nylon, could be successfully used as the carrier in place of silk fibroin.

Theoretical Study on the Mechanism of the Aromatic Substitution

Abstract: The mechanism of the aromatic substitution was studied on the basis of the energy level diagrams determined for both the aromatic molecule and the reagent. From the consideration of the relative heights of the highest occupied and lowest vacant orbitals of the former to those of the latter, it was deduced that a large electron transfer occurs at some stage of the reaction from the aromatic molecule towards the reagent for the electrophilic substitution and in the reverse direction for the nucleophilic substitution. In connection with this electron transfer mechanism, it was expected that the orientation rule observed with the aromatic substitution can be explained by free valency values of the aromatic cation, neutral molecule and anion for the electrophilic, radical and nucleophilic substitutions respectively. It was shown that this expectation is fully satisfied for various aromatic substitutions.

The Study of the Adsorption of Detergents at a Solution-Air Interface by Radiotracer Method. III. The Effect of Inorganic Electrolytes on the Adsorption of Sodium Dodecyl Sulfate

Abstract: The direct measurement of the adsorption of 35S labelled dodecyl sulfate ion at the solution surface and the measurement of the surface tension were carried out on the aqueous solutions of sodium dodecyl sulfate containing a given concentration of an excess salt. The salt concentrations studied were 0.01, 0.1, 0.3, 0.5 and 1N for sodium chloride, and 0.1 N for potassium-magnesium, manganous and aluminum chlorides. 1. The adsorption of dodecyl sulfate ion reaches equilibrium within one minute for all the systems under investigation. 2. The presence of excess of salt gives rise to the remarkable increase in the adsorption of dodecyl sulfate ion, but at the concentrations of excessive salts of about 0.1 N or more, the effects of the concentration and nature of the salts on the adsorption of dodecyl sulfate ion are not so appreciable. 3. The adsorption of dodecyl sulfate ion was well expressed by the Gibbs adsorption equation of n=1 for the systems under investigation.