NITRATION STUDIES. PART I. CATALYTIC EFFECTS IN VAPOR PHASE NITRATION. PART II. NITROHALOGENATION OF NEGATIVELY SUBSTITUTED OLEFINS WITH

NORMAN WESTON STANDISH, Purdue University

Abstract

Standish, Norman W., Ph.D., Purdue University, January 1960. Nitration Studies. I. Catalytic Effects in Vapor Phase Nitration. II. Nitrohalogenation of Negatively Substituted Olefins with Mixtures of Dinitrogen Tetroxide and Halogens. III. Preparation of 1,1,1-Trichloro-3-nitro-2-alkenes. Major professor; G. Bryant Bachman.Part I. Catalytic effects in vapor phase nitration. This investigation was concerned with improving the vapor phase nitration process. Specifically, the vapor phase nitration of propane with nitric acid or nitrogen dioxide was studied in the presence of additives such as organic peroxides, hydrogen peroxide, and ozone. The effects of exposure of the nitration mixtures to physical sources of energy such as ultraviolet irradiation and silent electrical discharge were also studied. Although peroxides and silent electrical discharge gave no improvement in yields, ultraviolet irradiation gave slightly improved yields of nitro paraffins and altered the distribution in favor of the higher molecular weight nitro paraffins. Ozone was outstanding in its ability to promote nitration and reduce oxidation to carbonyl compounds. Thus, the conversions to and yields of nitro paraffins found with ozonized were considerably higher than those found with an equivalent amount of oxygen.Part II. Nitrohalogenation of negatively substituted olefins with mixtures of dinitrogen tetroxide and halogens. This investigation was primarily concerned with the liquid phase reaction of negatively substituted olefins with mixtures of dinitrogen tetroxide and halogens. Specifically, these studies showed that vinyl cyanide, 1,2-dichloroethylene, 1,1-dichloroethylene, trichloroethylene, and 1-chloropropene react with nixtures of dinitrogen tetroxide and chlorine (or bromine) to give halonitro ethanes to the practical exclusion of halonitrato ethanes. The structures of these compounds were determined by hydrolysis to halogenated acetic acids, and by the products formed in their reactions with sodium anthranilate. From the products and orientations observed certain conclusions concerning the ability of the substituted olefin to induce free radical vs. ionic additions have been made.Part III. Preparation of 1,1,1-trichloro-3-nitro-2-alkenes. This investigation was concerned with developing a process for the preparation of nitro olefins by a continuous process. Specifically, a vapor phase condensation of chloral with nitro paraffins was studied at 360° over over a magnesium sulfate-amine catalyst, and was found to give the corresponding trichloro- nitro olefins, and substantial amounts of the trichloronitro alcohols. Derivatives of these products were also prepared.

Degree

Ph.D.

Subject Area

Organic chemistry

COinS