The fluorescent whitening agents in (3) were synthesized. Specimen solutions of 2.00 × 10-5mol/l of (3) were irradiated at 30±0.2°C for one hour with blacklight (360 mμ). Before and after the irradiation, the uv absorption spectra, fluorescence spectra and the tic of the solutions were examined. R-C_??_O-H-N-SO3Na-CH_??_CH-SO3Na-H-N-C_??_O-R Results : With the R's belonging to unconjugated substituent groups like methyl, n-propyl, n-heptyl, benzyl, and cyclohexyl, (3) proved unstable to uv light, showing a photochemical change which was presumed to be trans-cis isomerization. On the other hand, with the R's belonging to conjugated substituent groups, like phenyl, o-and p-methoxyphenyl, o, m and p-chlorophenyl, o-and p-nitrophenyl, vinyl, and styryl radicals, (3) proved stable to uv light. Fluorescence intensity was remarkably lower in the second group of substituents than in the first.
An attempt to prepare N-acetylphosphoroamidate by the reaction of triethyl phosphite with N-bromoacetamide in ether was unsuccessful, and the reaction did not produce acetonitrile. In this reaction it was found that diacetamide hydrobromide and triethyl phosphate were formed neanly quantitatively. It seemed reasonable to assume that the phosphonium intermediate in this reaction is extremely unstable against moisture. The infrared and mass spectra of diacetamide hydrobromide were also determined.
This paper describes the results obtained in applying the Ritter reaction to syntheses of N-substituted acrylamides. N- [1- (p-chlorophenyl) ethyl] acrylamide (1a), N- [1- (p-chlorophenyl) isopropyl] acrylamide (1c) and N-[1- (p-chlorophenyl) -1-methylpropyl] acrylamide (1d) were prepared by the reaction of acrylonitrile and each one of p-chlorophenylmethylcarbinol, p-chloro-α, α-dimethylbenzyl alcohol and 2- (p-chlorophenyl) -2-butanol in the presence of concentrated sulfuric acid. Similarly, N- [1- (p-chlorophenyl) ethyl] methacrylamide (1b) was prepared from methacrylonitrile. When the reaction was carried out with N- (hydroxymethyl) -p-toluamide, N- (hydroxymethyl) -p-chlorobenzamide and N- (hydroxymethyl) -2-naphthamide, three methylene-bis-amides, i. e., N- (p-toluamidomethyl) acrylamide (3e), N- (p-chlorobenzamidomethyl) acrylamide (3f) and N- (2-naphthamidomethyl) acrylamide (3h) were obtained. Reaction of N- (hydroxymethyl) acrylamide with benzonitrile or with methacrylonitrile could be achieved, and N-benzamidornethyiacrylamide (5) or N-acrylamidomethylmethacrylamide (6) was prepared. Benzoyl peroxide catalyzed polymerization of (1a), (1b), (1c) and (1d) gave vinyl polymers. Vinyl polymerization of (3e), (3f), (3h) and (5) were also investigated by potassium persulfate catalyst. It was recognized that sodium tert-butoxide catalyzed polymer of (1a), (1d), (3f), (3h) and (5) were hydrogen migrated polymer at least predominantly.
The syntheses and some reactions of β, β-dichlorovinyl sulfones were investigated. The condensation of arylsulfonyl chloride with vinylidene chloride followed by dehydrochlorination with the aid of triethylamine gave the following ; β β-dichlorovinyl-phenyl sulfone (mp 4851°C), β, β-dichlorovinyl-p-tolyl sulfone (mp 5053°C), β, β-dichlorovinyl-2, 4-dimethylphenyl sulfone (mp 4548°C) and β, β-dichlorovinyl-2, 5-dimethylphenyl sulfone (mp 112115.5°C). The reaction of β, β-dichlorovinyl sulfone with aniline or with p-chloroaniline could be achieved, and the corresponding β, β-dianilinovinyl sulfone or β, β-di (p-chloroanilino) vinyl sulfone was prepared. β, β-Di (p-nitrophenoxy) vinyl sulfone was also obtained by the reaction of β, β-dichlorovinyl sulfone with sodium p-nitrophenolate, suspended in dimethyl sulfoxide.
Alkylenedibiguanides (C2C10, except C3) were prepared from alkylenediamines by the guanyl-O-alkylisourea method. Thus, alkylenediamines readly reacted with guanyl-O-methylisourea salts in an aqueous solution at room temperature to give the corresponding alkylenedibiguanides salts in good yield. Further, some aminoalkylbiguanide salts could be prepared by this method, under suitable reaction conditions. Chemical properties of these compounds were described.
Usually azo compounds are identified by cleavage of azo group by reduction, followed by identification of produced. amines This method, however, can not be successfully applied to azo dyes with pyrazolone component, because the resulting amino-pyrazolones are unstable and change rapidly into very complex rubazonic acids. On the other hand, when the hydroxyl group at 5-position of pyrazolone was substituted by chlorine with phosphorous oxychloride, the resultant amino pyrazole derivatives were stable. By this way identification of pyrazolone component can be accomplished.
Treatment of benzonitrile oxide, p-nitrobenzo-and m-nitrobenzonitrile oxide and 5-nitro-2-furocarbonitrile oxide with triphenylphosphinebenzoylmethylene afforded the corresponding 5-phenylisoxazoles instead of the expected keteneimines and oximes. The mechanism for the formation was discussed.