THE RÖLE OF MERCURIC NITRATE IN THE “CATALYZED” NITRATION OF AROMATIC SUBSTANCES.⁴ [FIRST PAPER.]

Abstract

the same two stages really exist, but that iron catalyzes the secondary reaction so that it is practically instantaneous. Reactions.It has long been known that perchloro-mercaptan can be reduced by silver dust,1 iron and acetic acid,2 or stannous chloride, or tin and hydrochloric acid3 to thiophosgene, according to the reaction CSCI4 + SnCl2 -CSC12 + SnCl4. When this reduction was tried with zinc and hydrochloric acid the perchloro-methyl-mercaptan disappeared completely; apparently it was reduced to methane, which escaped as gas. With iron and hydrochloric acid, a mixture of thiophosgene and carbon tetrachloride is obtained. When perchloro-methyl-mercaptan was refluxed with iron filings it gave nothing but carbon tetrachloride. An attempt to replace one of the chlorine atoms by fluorine failed. When perchloro-methylmercaptan was refluxed with zinc fluoride the inner tube of the condenser was rapidly and deeply etched, and the product was nearly pure carbon tetrachloride.Summary. A convenient method of preparing perchloro-methyl-mercaptan with Yields as high as 65% has been worked out, and some of the reactions of this compound have been studied. Baltimore, Md.

THE OXYNITRATION OF BENZENE TO 2,4-DINITROPHENOL1

“…Abbreviations: DNP = 2,4-dinitrophenol; NB = nitrobenzene; DNB = crude dinitrobenzene. 6 The major portion of this fraction was 2,4,2',4'-tetranitrodiphenylamine.…”

Mercuric salt catalyzed nitration of toluene

“…Early workers reported that the yield of nitrobenzene approached 50% when the oxynitration reaction was carried out in concentrated nitric acid. 5 Tsutsumi and Iwata and Osawa and his co-workers studied the effects of other metal oxides and metal nitrates on nitration with nitric acid.6™8 However, only mercuric oxide and mercuric nitrate accelerated the reaction importantly and altered the isomer distribution.6'7•9 Komoto and his associates examined the mercuric acetate catalyzed nitration of toluene using concentrated nitric acid in acetic acid at 80 °C.10 Under these conditions, the catalyzed reaction produced the isomeric nitrotoluenes in good yield. Several investigators have proposed that electrophilic aromatic mercuration is the first step in this reaction.7•10 The nature of the subsequent steps in the process remains unclear.…”

Oxynitration of Benzene to Picric Acid

“…It was also reported that the same oxynitration: takes place with benzoic acid (80). Accounts, more or less complete, are available of work on this reaction in several countries during the period 1914 to 1918 (3,6,7,9,10,11,19,20,22,23,24,26) and shortly thereafter (4,13,32). Blechta and Patek (4) have extended the oxynitration reaction to toluene, and Davis (9) to naphthalene.…”