Photochemical and thermal transformations of azomethine imines

The thermal and photochemical fragmentations of a few bisazoalkenes have been investigated. 2-Phenyl-4,5-disubstituted-1, 2,3-triazoles were obtained both in the thermolysis and photolysis of 1, 2-bisphenylazo-(4, 4′-dichloro) stilbene, 1, 2-bisphenylazo(4, 4′-dimethoxy)stilbene, 1, 2-bisphenylazocyclohexene and o-(phenylazo) phenyldiazocyanide. Both 2, 3-bisphenylazo-2-butene and 1, 2-bisphenylazoethylene failed to undergo either photolysis or thermolysis in the expected manner. However, 2, 3-bisphenylazo-2-butene underwent an acid-catalysed valence isomerisation to anhydro 1-phenylimino-2-phenyl-4, 5-dimethyl-1, 2, 3-trizolium hydroxide, which on photolysis gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. The same iminotriazolium intermediate gave a cycloadduct, 2, 6-diphenyl-3, 3a-dimethyl-4, 5-dicarbomethoxypyrazolino [2.3.c][1.2.3] triazole, on treatment with dimethyl acetylenedicarboxylate, whereas treatment with carbon disulphide gave 2-phenyl-4, 5-dimethyl-1, 2, 3-triazole. Both photolysis and thermolysis of C-biphenylene-N^α(4-chlorophenyl)-N^β-cyanoazomethine imine gave 9-fluorenone-N- (4-chlorophenyl) anil. Photolysis of 1, 2-bisphenylazoacenaphthylene in methanol gave acenaphthenequinone monophenylhydrazone.     

Deuterium exchange of 4-pyrimidones and 4-pyrimidthiones

The hydrogen-deuterium exchange of H-2 in 4-pyrimidone, a number of 1- and 3-alkyl-4-pyrimidones and several of their thione analogs in deuterium oxide at moderate temperatures is reported. This reaction is apparently not susceptible to acid or base catalysis. Cations of the 4-pyrimidones were found not to exchange H-2 at all in acid media. Catalytic amounts of bases do not alter the exchange rates whereas more concentrated alkali decompose the pyrimidone. However, 1,4(3,4)-dihydro-1,3-dimethyl-4-oxopyrimidinium iodide (and its 6-methyl analog) exchange H-2 quite rapidly in neutral deuterium oxide, almost instantly when triethylamine is added as a catalyst, and very slowly in dilute solutions of deuterium chloride in deuterium oxide. Mechanisms are proposed to account for these phenomena.     

Studies on the solvent extraction of uranyl bis(dibenzoylmethane)

Studies of unmasked and masked extractions of the uranyl bis(dibenzoylmethane) dibenzoylmethane chelate from aqueous solutions into chloroform containing dibenzoylmethane have been made. Aqueous media containing the following were studied: perchlorate, fluoride, acetate, oxalate, citrate, tartrate, nitrilotriacetate, ethylenediaminetetraacetate. A number of fundamental constants have been determined, these values allowing theoretical interpretations of several of the systems to be made.     

Ionization constants for deuterium oxide in deuterium oxide-organic mixtures

A potentiometric method using a glass electrode has been applied to determination of ionization constants for deuterium oxide (D₂O) in binary mixtures of D₂O with dioxane, tetrahydrofuran, acetone, dimethylsulfoxide, CH₃CH₂OD, and CH₃OD at 25°C. The results are compared with values of ionization constants for H₂O obtained previously in the corresponding H₂O-organic mixtures, and the isotope effect is shown to be small. Further calculations with the D₂O results show that the first five solvents mentioned above are neither appreciably acidic nor basic in D₂O solution, but that CH₃OD shows slightly acidic behavior (pK_a=16.0±0.3).     

Quinazolines. VII. Synthesis of 1,3-Diamino-5,6-dihydrobenzo[f]quinazolines

Eighteen new 1,3-diamino-5,6-dihydrobenzo[f] quinazolines ( 6 , R. = alkyl, Cl, MeO) were synthesized via the condensation of appropriate 2-tetralones with cyanoguanidine under fusion conditions. Methods were developed for the preparation of a number of heretofore undescribed 2-tetralones as precursors. The final products can be viewed as conformationally rigid analogs of pyrimethamine ( 2 ), and are of interest as inhibitors of dihydrofolate reductase and as potential antimalarial and antitumor agents.     

Study of (π-C5H5)2Ti(CH3)Cl and (π-C5H5)2Ti(C6H5)Cl in soluble Ziegler catalysts

Soluble ethylene polymerization catalysts derived from (π-C₅H₅)₂Ti(R)Cl and R ′AlCl₂, where R = methyl or phenyl and R ′ = methyl or ethyl, were studied both by polymerization kinetics at 0°C and by diagnostic experiments. It was found that the first insertion of ethylene into the Ti? R bond is difficult when R = methyl or phenyl, and for this reason these catalysts show a different overall behavior than when R = ethyl or higher alkyl.     

Theory of absorption and emission of radiation in molecular collisions: Semiclassical model

A semiclassical transition amplitude is derived for electronically inelastic molecular collisions in the presence of an intense electromagnetic field. The calculation of this amplitude involves the integration of classical trajectories for nuclei moving on effective potential energy surfaces. These surfaces, which exhibit an avoided crossing due to the coupling through the dipole interaction around the resonance nuclear configuration, are analytically continued to their complex intersection points, where trajectories switch surfaces. Other parts of these surfaces are similar to the field-free adiabatic surfaces, where one is shifted by ?ω. Metastable states, formed at some collision energies, are suggested in the field which are absent in the field-free system.