David H. Rosenblatt

Organic Explosives and Related Compounds

For much of this century production and usage of explosives and propellants have been responsible for release to the environment of a variety of energetic organic nitro compounds. This chapter covers the compounds of greatest importance; their uses are indicated and methods for their manufacture or laboratory synthesis are summarized. Those physicochemical properties of greatest utility in environmental risk assessment are identified and listed. Analytical methods are described briefly, with references given to more detailed literature. For the more extensively studied compounds, the microbiological and chemical transformations known to take place in the laboratory and in the environment and the metabolic transformations observed in animals and man are discussed. Toxic manifestations in mammals, humans, fish and other aquatic organisms, as well as threshold levels for these effects, are summarized. While the process of utilization of available experimental data to develop criteria and standards to assure protection of human health and preservation of the biosphere is in its infancy and changing rapidly, a short summary of criteria currently accepted in the U.S. for certain of the munitions compounds is presented.

INFLUENCE OF CHEMICAL STRUCTURE ON THE RATE OF AZO COUPLING AND ITS SIGNIFICANCE IN HISTOCHEMICAL METHODOLOGY

Reliability of enzymatic localization in tissue sections by the simultaneous coupling techniques is dependent to a great extent upon the speed of coupling. Therefore, the influence on coupling rate of the structure of the diazonium ion and of the coupling component was studied. Electro-negative groups in the diazonium ion increase the rate of coupling, while the same groups in the coupling component decrease the rate. Electro-positive groups in the coupling component accelerate coupling, but slow it when present in the diazonium ion. The relation of coupling rate and electro-negativity of the substituents in the diazonium ion follows Hammetts equation (8). Although the relations is linear on coupling with aromatic hydroxy compounds, it is not so with aromatic amines. The most active diazonium ions showed no increase in coupling rate with aromatic amines. This suggests that for those enzymes hydrolyzing an ester link, increase of coupling rate might be accomplished by modifying the structure of either the coupling component used in the substrate or the diazonium salt. However, for enzymes splitting amide linkages, the only possibility of improving the localization is by modifying the structure of the coupling component.

PAPER PARTITION CHROMATOGRAPHY OF MIXTURES OF CHLORIDE, CHLORITE, CHLORATE AND PERCHLORATE.

Abstract : An improved method for qualitative analysis of mixtures containing chloride, chlorite, chlorate, and perchlorate has been developed. This method utilizes paper partition chromatography and differential spray reagents for location of the separated spots. (Author)

Detection of monobasic phosphorus acid esters by conversion to cholinesterase inhibitors

Abstract Many monobasic acids of quinquevalent phosphorus form cholinesterase inhibitors when exposed to ketene. Based upon this finding, a sensitive test to detect the presence of these compounds on filter paper has been developed. Seventeen out of nineteen of these acids tested gave positive results. Negative results obtained with the remaining two are attributable to steric factors or to the high hydrolysis rate of the acetylated product. Only one of eighteen phosphorus compounds other than the monobasic acids examined, namely n -butylphosphonic acid, gave a positive test; an explanation is offered to account for this exception.

Use of debenzylation of quaternary benzylammonium salts in the synthesis of α-deuteriated tertiary amines

Simple syntheses are described of two deuteriated tertiary amines, namely NN-dimethyl-p-nitro[α-2H2]benzylamine and tri([1-2H2]ethyl)amine. The deuteriation step in the preparation of the former amine involves a selective exchange of the benzyl protons in dimethylbis-(p-nitrobenzyl)ammonium bromide by treatment with alkaline deuterium oxide. The second preparation requires [1-2H2]ethyl iodide, which is converted into benzyltri([1-2H2]ethyl)ammonium iodide. The final, key step common to both syntheses is the debenzylation of the quaternary ammonium ion.