To investigate the relation between the solubility of inorganic salts and the dielectric constants of solvents, the solubility of silver bromate in tetrahydrofuran-water mixed solvent was determined at 20°, 25° and 30°C, respectively. The logarithm of solubility is almost reciprocally proportional to the dielectric constant of the solvent in the region of the higher dielectric constant. But no linear relation was found in that of the lower dielectric constant of tetrahydrofuran-water mixed solvent. Also, the solvation radius of silver bromate was calculated applying the above-mentioned data. The solvation radius is about 1 Å at each temperature.
Hydroformylation of methylacrylate in the presence of dicobalt octacarbonyl was investigated by paying a special attention to the effect of varying ratios of carbon monoxide to hydrogen on the rate. The rate attains the maximum value at a certain partial pressure of carbon monoxide, and increases with the increasing partial pressure of hydrogen. The tendencies agree with the results obtained by G. Natta on the hydroformylation of cyclohexene. The rate equation proposed by A. R. Martin with respect to the rate of hydroformylation of di-isobutene can represent the tendencies observed in the present results. In the presence of iron pentacarbonyl, methylacrylate has been found to be reduced to methylpropionate under high pressure of hydrogen containing carbon monoxide. The reduction becomes more difficult with the increasing partial pressure of carbon monoxide, but was made catalytically neither by an iron catalyst reduced from iron oxide nor by the one produced by the thermal decomposition of iron pentacarbonyl.
The various methods for obtaining straight lines were examined for the tie-line data investigated at several temperatures near the critical solution temperature for binary mixtures of the solute and the solvent, and the following results were obtained. 1. The Hand plot and the Othmer and Tobias plot which are useful for the systems containing one partially miscible pair are unsatisfactory for the systems containing two partially miscible pairs. 2. The method proposed by Brown and the method by Conway and Philip which have been said to be applicable for the systems containing the formation of two pairs of partially miscible liquids do not give good results for the systems at temperatures near the critical solution temperature for binary mixtures of the solute and the solvent. 3. If a plot is made of the logarithm of the ratio of the concentration of the diluent in the diluent phase to the concentration of the solvent in the solvent phase against the logarithm of the concentration of the diluent in the diluent phase, a straight line will be obtained not only for systems containing two partially miscible pairs, but also for systems containing one partially miscible pair.
The magnetic susceptibility of nine nitroso compounds, as solids and as solutes, were measured by the Gouy method. The constant for the nitroso group attached to a carbon atom was found to be paramagnetic of the order of 10 units. The author suggested that the second term in Van Vleck’s equation for the diamagnetism of a molecule is dominant in this case. Some quinones and their monoximes were also measured, and it appeared that the ability of the oxime group to localize aromatic electrons is less than that of the carbonyl group. In addition, the structure of nitrosodialkylaniline hydrochloride was discussed from the magnetic standpoint.
(1) The reaction of diphenylethylene, atropic acid, and styrene with the mixture of hydrogen bromide and oxygen were studied. In the case of diphenylethylene, diphenylbromomethane, ω-bromoacetophenone, diphenylethylene dibromide, phenol and carbon dioxide were obtained as reaction products. A reaction mechanism was proposed to explain how these compounds were produced. (2) In the case of atropic acid, a large amount of α-hydroxy-β-bromohydratopic acid and a small amount of ω,ω-dibromoaceto phenone and of carbon dioxide were obtained. A consideration on the mechanism of the formation of these products was given on the basis of the identified products and their semiquantitative estimation. (3) Addition of hydrogen bromide to atropic was carried out under various conditions. No reversal of the direction of addition of hydrogen bromide was observed contrary to the previous reference. (4) The reaction of styrene with the mixture of hydrogen bromide and oxygen added an example yielding a phenolic substance ia the reaction.
1) When Erlenmeyer’s β-phenylserine ethyl ester was reduced with Raney nickel catalyst, DL-threo-1-phenyl-2-benzylideneamino-1, 3-propanediol (a Schiff base) was obtained as a main product. The structure was demonstrated by means of its infrared and ultraviolet absorption spectra. 2) It was found that DL-threo-1-phenyl-2-benzylideneamino-1, 3-propanediol gave DL-threo-N-acetyl-2-phenyl-4-(α-hydroxybenzyl) oxazolidine on acetylation with acetic anhydride. 3) The condensation products of DL-threo-1-phenyl-2-amino-1, 3-propanediol and DL-threo-1-p-nitrophenyl-2-amino-1, 3-propanediol with benzaldehyde, o-, m- and p-nitrobenzaldehyde were prepared and acetylated to give corresponding oxazolidine derivatives, which failed to hydrolyze under Kunz’s conditions. Infrared and ultraviolet absorption spectra of some of these compounds were observed. Acetylated derivatives failed to show the characteristic absorption of (Remark: Graphics omitted.) bond in the 1660–1610 cm−1 region. 4) DL-Chloramphenicol was synthesized from DL-threo-N-acetyl-2-phenyl-4-(α-hydroxybenzyl)oxazolidine.
1. The mucilage of Gloiopeltis furcata has been investigated by the complete methanolysis method. 2. 3,6-Anhydro-L-galactose dimethylacetal and methyl D-galactoside have been isolated from the methanolysate. In addition, L-galactose has also been isolated in the form of the crystalline DL-galactose diethylmercaptal. 3. The yields of the isolates have indicated that the mucilage used contains 3, 6-anhydro-L-galactose, D-galactose and L-galactose in the approximate molar ratio of 8:12:1.
(1) When the N-acetyl ethyl ester of Erlenmeyer’s phenylserine was reduced with hydrogen over Raney nickel catalyst, ethyl DL-threo-N-acetyl-β-cyclohexylserinate was obtained in crude yields as high as 86.8 %. Subsequent hydrolysis with dilute hydrochloric acid afforded DL-threo-β-cyclohexylserine, which gave hexahydrobenzaldehyde by periodate oxidation. (2) Raney nickel reduction of ethyl DL-threo-β-cyclohexyl-serinate afforded DL-threo-2-amino-1-cyclohexylpropane-1, 3-diol. The aminoalcohol was converted into DL-threo-2-dichloroacetamido-1-cyclohexylpropane-1,3-diol, a chloramphenicol analogue.
The general expression for the azeotropeforming power of binary solution has been derived and the conditions for azeotrope existence presented. The quasi-crystalline model has been adopted for the solution, which is assumed to be a strictly regular solution at an azetropic point and an explicit representation for interaction energy of component molecules introduced. Azeotropic mixtures have been grouped into four classes according to the type of molecular interaction and the azeotrope-forming power (molecular interchange energy) has been calculated and discussed.