N-Acetyl and N-benzoyl lactams consisting of a five-to-seven-membered ring were found to be good acylation reagents. Several amines were acylated with these reagents to give the corresponding amides in good yields. When N-benzoyl-2-pyrrolidone was used, ring-opened by-products were obtained by the reaction with a secondary amine, such as pyrrolidine and piperidine. Tosylalanyl-2-pyrrolidone reacted with primary amines to produce the corresponding tosylalanine amides. The alanine methyl ester reacted as a primary amine with tosylalanyl-2-pyrrolidone to afford a dipeptide.
Propylene has been pyrolyzed in a flow system over a wide range of conditions (temperature, 800∼1400°C; contact time, 4.4×10−4∼2.3 sec.; pressure, 40∼160 mmHg) to find suitable conditions for producing methylacetylene (and allene) and for obtaining data concerning the distribution of pyrolysis products. Under proper conditions, the pyrolysis occurred without any appreciable production of tarry and carbonaceous materials. High temperatures (1200∼1300°C), short contact times (millisecond order; conversions below 30%), and low pressures (below l00 mmHg) were found to required for the good production of methylacetylene-allene. A methylacetylene-allene yield of 38 mol. per 100 mol. of propylene pyrolyzed was realized at 1200°C, 50 mmHg pressure (partial pressure of propylene, 40 mmHg), and 24% conversion (contact time, 1.7 msec.). The other gaseous products were found to be methane, ethylene, hydrogen, acetylene, 1-butene and butadiene, in decreasing order.
A study has been made of the mechanism of the pyrolysis of propylene at high temperatures (800∼1400°C). Of the gaseous products, hydrogen, methane, ethylene, allene, and 1-butene, obtained in the yields of 25, 43, 40, 27, and 9 mol. per 100 mol. of propylene pyrolyzed (3% conversion) respectively, have been found to be the primary products, while methylacetylene, acetylene, and butadiene, obtained in the yields of 9, 4, and 2 mol. respectively, have been found to be the secondary products. In view of the results of the pyrolysis of allene itself, even at a low conversion of 3%, allene appears to undergo considerable secondary reactions, such as isomerization to methylacetylene, addition to propylene and allyl radicals, and decomposition, for example, to acetylene and methane via methylacetylene. On the basis of the observed results, free-radical mechanisms have been proposed for the primary reactions and main secondary reactions. The mechanism for the primary decomposition reaction is a chain process in which the chain is initiated by the reaction C3H6→C3H5· (allyl radical) + H, and is, via the chain-propagating step, terminated by two types of reactions, C3H5·+H→ C3H6 and C3H5· + CH3·→1-C4H8. The formation of allene-methylacetylene has been satisfactorily explained by considering secondary reactions.
The thermal and photo-isomerizations of crystalline cis-azobenzene have been studied by infrared spectrophotometry in the temperature range of 36∼58°C, It has been found that the thermal isomerization follows Prout Tompkins’ law, and the values of k3 at 36, 50 and 58°C have been estimated. The Arrhenius plot of K3 is linear, and the activation energy of k3 is 31.3±0.3 kcal./mol. Pre-irradiation with a mercury lamp shortens the induction period, but it does not change the value of k3. On the other hand, the value of k3 is affected by the degree of grinding of azobenzene crystals. In this case, the activation energy is not altered by crystal grinding. The photo-isomerization at 12°C, in contrast to the case of thermal isomerization, has no induction period. However, the trans→cis photo-isomerization does not occur even if the crystal is treated by X-ray or by γ-ray preirradiation.
The reactive complex produced by the reaction of trimethylaluminum with diphenylamine has been studied by the ultraviolet absorption and proton magnetic resonance methods. The ultraviolet absorption of the complex has shown two bands, at 228 mμ and 274 mμ, in cyclohexane. Proton magnetic resonance spectrum of the complex has been shown to consist of two groups of peaks, with an intensity ratio of approximately 5:3 and with chemical shifts of 2.90 p.p.m. and 10.58 p.p.m. These shifts have been assigned to phenyl protons and methyl protons respectively. In the mixture of trimethylaluminum and the complex, an exchange of methyl groups occurs. The structure of the complex has been concluded to be dimeric through two nitrogen bridges, as is shown in formula II.
Fragment ions with high kinetic energies have been produced from methanol by electron impact, as in the cases of many hydrocarbons. Assuming that a fragment has a rotational energy of the order of 0.5 eV. most of the high-energy ions from methanol can be ascribed to a doubly-charged molecule ion that dissociates into two singly-charged fragments.
Quiram and Biller’s freeze-out method, originally devised to determine hydrocarbons contained in air above l0 p.p.m. and using a mass spectrometer, was tried on a trace (down to 1/100 p.p.m.) of mercury vapor in atmosphere ; it was proved to give satisfactory results. The freeze-out procedure was then slightly modified. To collect the pollutants, the air sample was circulated automatically for ten minutes through the freezing-out trap instead of repeatedly handling the stopcocks. By this procedure, a blended air sample containing various pollutants above 10 p.p.m. have been analyzed. The precision is about ±10%.
A simple and accurate spectrophotometric method with the iron(III) -1, 10-phenanthroline reagent has been established for the determination of a small amount of l-ascorbic acid ; it has been applied to the measurement of the catalytic effects of metal ions on the autoxidation of l-ascorbic acid.
The stability constants of various kinds of copper complexes have been estimated on the basis of the decrease in the catalytic activity of copper (II) in the presence of chelating agents. The rate constant, k, has been found to be inversely proportional to log (1+Ks[Y]n).
Several kinds of products have been found to be formed from mixtures of cyclohexene and acetaldehyde by the irradiation of γ-rays, electron beams, and ultraviolet. Both the yields and the kind of product seem to depend on the type of radiation because of their dose rate and bond-dissociating power.
The thermal decomposition of hexamminecobalt(III) chloride has been investigated by thermogravimetric, polarographic and infrared spectroscopic method. The results indicate that the reaction is initiated by the electron transfer from either a ligand molecule or an outersphere ion to the central cobalt atom, forming a less stable cobalt(II) complex, which immediately dissociates ammonia molecules and undergoes decomposition.
The vacuum ultraviolet absorption spectra of anilne, N-methylaniline, N-ethylaniline, N,N-dimethylaniline, N,N-diethylaniline and N-n-butylaniline have been measured in the vapor phase by a recording vacuum ultraviolet spectrophotometer, with which the absorption measurements have been extended down to 1500 Å. Some new bands have been found in the vacuum ultraviolet region, and in total five π→π* transtion bands with molar extinction coefficients larger than 1500 have been observed commonly for the anilines. In order to clarify the nature of these bands, a theoretical treatment has been made by considering the configuration interaction among the ground, locally excited and charge-transfer configrations. An excellent agreement has been obtained between the experimental and the calculated result. It has been concluded the the anilines studied here exhibit intramolecular charge-transfer bands characteristic if the electron trasfer interaction between the substituent and benzene ring.
The distribution of the chemical species containing phosphorus-32 formed by the (n,γ) reaction has been studied for several phosphates as functions of the irradiation conditions in a reactor. The variation in the distribution has been discussed in connection with the radiation annealing process during irradiation, and a comparison of the distribution of the chemical species containing phosphorus-32 by three separation methods has been made. By means of the analysis of the variation curves of the distribution of the chemical species containing phosphorus-32, the apparent rate constants have been estimated. It has been suggested that the variations in the distribution may be approximately expressed by radiation annealing processes, and that they are affected by pile factors.
The dielectric constant and loss of single crystals of DL-[Co(en)3]Cl3·nH2O have been measured between −150°C and room temperature in the frequency range 40 c./s. and 3 Mc./s. The water content, n, was varied from 0.27 to 3.6. The anomalous dispersion and relaxation absorption due to the hindered rotation of water have been observed and they are strongly dependent on n. The activation energies for the relaxation absorption have been determined for different n values and for different orientations of the crystals. A molecular mechanism for the absorption has been presented on the basis of the zeolitic nature of the water molecules in the crystal as determined previously from structural and thermodynamics investigation
In order to study the effect of high pressure on the electrical conductivity of organic semiconductors, the band structure of the anthracene crystal has been calculated at atmospheric pressure and also at 160 kilobars, using the treatment of the tight-binding approximation. The total band widths of both electrons and holes at 160 kilobars are 5∼6 times as large as those at atmospheric pressure. Although the mobilities of both carriers, on the whole, increase in magnitude by several tens times at 160 kilobars, the sharp drop in the resistivity at high pressure may be due mostly to the great increase in the concentrations of the charge carriers (103∼104 times).
Poly (N-vinyl carbazole) (specific resistivity, above 1017Ω cm.) gives a dark-green charge transfer complex with tetracyanoquinodimethane. The specific resistivity of the complexes at room temperature is 1014∼1016Ωcm. and the band-gap energy is 1.1∼1.5 eV. The film-forming property of poly(N-vinyl carbazole) is retained in the complex. The charge transfer band is observed at about 620 mμ.