Blue Brilliant colours of new type were synthesized by combination of Blue azocolours and Fluorescent whitening agents. For example, Cl-Cl-Cl=H2N_??_-S-CH=CH_??_S-NH2→ [Cl-Cl-HN_??_S-HC=] 2_??_H2N_??_-NHCOCH3 (NaOH) [H2N-_??_-NH-HO-NH_??_S-CH=] 2Fluorescent whitening agents-Cl-Cl-Cl+ [H2N-OH-N-S-S=N_??_OCH3] 2_??_ : -C-N=C-N=C-N= S : SO3Na [Cl-Cl-NH-OH-N-S-S=N_??_OCH3] 2Blue azo colour_??_ [H2N_??_NH-HO-NH_??_S-CH=CH_??_-NH-S_??_NH_??_-NH-OH_??_HO-NH_??_S OH-S-N=N-OCH3] 2 Blue Brilliant Colour VI. Although these Colours Were found to have weak affinity for fiber, their aqueous solutions have considerable brilliancy and fastness for light and γ-ray.
Until the completion of this investigation 1, 7-Cleve acid has been produced in an industrial scale by sulfonation of naphthalene, followed by nitration and reduction. However, its separation from accompanying 1, 6-Cleve acid, Peri-acid and others is not so easy, and it has been difficult to obtain the acid in pure form enough for industrial use. The authors have succeeded in synthesizing the acid by sulfonation of 1-naphthol followed by hydrolysis and Bucherer reaction. (1) Hydrolysis of di-sulfonated naphthol to mono-sulfonic acid directly by use of the remaining sulfuric acid. (2) Addition of ammonia and ammonium bisulfite to the sodium 1-naphthol-7-sulfonate solution (obtained by sodation of calcium 1-naphthol-7-sulfonate solution separated by liming the mixture of the monosulfonic and sulfuric acid solution) and heating the mixture. The process is now established and has been already carried out since a few years ago.
In order to have a quantitative information about the products from formaldehyde by the Bucherer-Bergs synthesis, the reaction mixture was treated on a strong cation exchange resin and the major products were determined about the effluent and eluate. In the effluent : there was relatively large amount of hydantoic acid together with hydantoin and hydantoic amide. On heating, the former was increased while the latter two were decreased. In the eluate : glycine was found together with a little amount of aminoacetonitrile and glycinamide. The synthetic route of hydantoin is, of course, through the aminoacetonitrile, during the addition of carbon dioxide, some parts of aminonitriles was directly hydrolyzed to glycinamide and further to glycine.
In the previous paper, the products from formaldehyde by the Bucherer-Bergs synthesis was reported. In this paper, studies on the reaction about the effects of the reaction compositions and conditions was reported. Reaction of glycolonitrile and ammonium bicarbonate was studied and the result resembled to that of formaldehyde. When the mixture was refluxed with mineral acid, hydantoin was obtained in a 82% yield. In the case of formaldehyde the reaction temperature was elevated to give a rather higher yield of glycine. But the yield of glycine was at most 69% by direct heating at 170°C. It was considered that the driving force of the hydrolysis reaction stemmed from sodium carbonate, the equilibrium of the reaction had to be changed by the removal of the formed carbon dioxide. By this means, glycine was prepared in 86% yield which was as good as ordinary one using 2 moles of sodium hydroxide.
Eudalene was synthesized from bromobenzene as follows. 3- (p-bromobenzoyl) propionic acid (1) obtained by succinoylation of bromobenzene was converted to 7-bromo-1, 2, 3, 4-tetrahydronaphthalen-1-one (3) through 4- (p-bromophenyl) butyric acid (2). 7-Bromo-1-methyl-3, 4-dihydronaphthalene (5) obtained from (3) was dehydrogenated to give 7-bromo-1-methylnaphthalene (6) with sulfur. Eudalene (7) was obtained by the reaction of Grignard reagent from (6) with acetone, followed by reduction with hydrogen iodide.
The reduction of trihalogenomethylnitroalcohols (1) and trihalogenomethylnitrodiols (2) as the compounds containing trihalogenomethyl radical of potential therapeutic interest were examined by different methods. It was confirmed that (1) had been reduced to trihalogenometylhydroxylaminoalcohols (3) by catalytic hydrogenation but one of the chlorine atoms in (1) had been removed by hydrogenolysis and had been reduced to dihalogenomethylaminoalcohols (4) and (3) by electrolytic reduction. Trihalogenomethylaminoalcohols (5) and trihalogenomethylaminodiols (6) were synthesized by the reduction of (1) and (2) with tin and hydrochloric acid.