Kohji Matsui

Aromatic nucleophilic substitution—II : Intermediates in the reactions of 2,4-dinitro- or 2,4,5-trinitro-1-naphthyl ethyl ether with secondary amines and preparation of a spiro meisenheimer complex

Abstract The intermediates in the reactions of 2,4-dinitro-(2) or 2,4,5-trinitro-1-naphthyl ethyl ether (11) with secondary amines have been studied. In the reaction of 2 with piperidine, the NMR spectrum of the reaction system indicated the coexistence of the three species-starting material, Meisenheimer complex, and substituted product. In the reaction of 11 with piperidine or N-methyl-n-butylamine, the the NMR spectra of the reaction system indicated the presence of a Meisenheimer complex, but did not indicate the formation of a substituted product. In addition, the spiro Meisenheimer complex (9) was prepared from 1-[N-methyl-(2′-hydroxy)ethylamino]-2,4,5-trinitronaphthalene (8) and sodium methoxide.

Reactions of Aromatic Compounds in Molten Salts. I. Dimerization of Aromatic Amines in a Molten Mixture of AlCl3–NaCl–KCl

Aromatic amines underwent dimerization in a molten salt consisting of a mixture of AlCl3–NaCl–KCl. The reaction is an oxidative cationic polymerization but, in contrast with the reactions of the ordinary aromatic compounds which gave the corresponding polyaryls, in the cases of aromatic amines the reaction was regiospecific and stopped at the stage of biaryl to yield benzidine derivatives.

The reactions of 2-substituted 4-chloro-6-(2-hydroxy-1-naphthyl)-1,3,5-triazines with several nucleophiles.

The nucleophilic substitution reactions of 2-methoxy- and 2-diethylamino-4-chloro-6-(2-hydroxy-1-naphthyl)-1,3,5-triazines (1) with aniline, diethylamine, sodium azide, and sodium methoxide were carried out and compared with the reactions of the corresponding derivatives of 4-chloro-6-(4-hydroxy-1-naphthyl)-1,3,5-triazine (2) and 4-chloro-6-(1-naphthyl)-1,3,5-triazine (3). Compound 1 was found to be more reactive than the corresponding (2) and (3), not only in the reactions of a neutral molecule, but also in those of anionic species. The results of the reactions of neutral species are interpreted in terms of the difference in solvation toward the substrates; however, the loss of coplanarity between the naphthalene and triazine nuclei may be responsible for the high reactivity of Compound 1 in the reactions of anionic species.

Fluoresent Agents for Plastics (II): Photostabilities of the Fluorescent Agents in Solutions and in Plastics@@@樹脂中と溶液中のケイ光増白剤の光安定性

Photostability is one of the most important characters required for the practical use of a fluorescent agent. Photostabilities of fluorescent agents in plastics are expected to differ from those in fluid solutions, because of the differences in environmental conditions around the fluorescent molecules. The present paper reports these differences. The fluorescent agents employed in this work are the series of 7-amino-coumarin derivatives as described in the previous paper, and their photo-fading rates (photostabilities) were measured both in solutions and in plastics. The results were as follows : ( 1 ) The dependence of photostability on the nature of medium was rather remarkable in solutions than in plastics. ( 2 ) The fluorescent agents were considerably more stable towards UV-irradiation in plastics than in solution. However, correlations between two phases were described in ( 4 ) ( 3 ) Sometimes, the fluorescent molecule was found to act as a sensitizer for the photodecomposition of plastics. ( 4 ) Plots of the photofading rates in plastics against the corresponding fading rates in solution gave a straight line. The slope of this line depended on the nature of the plastics ; the slope is considered to be important for the practical use of the fluorescent agent for plastics.