Nitrate esters and

This change in editorial leadership has resulted, perhaps inevitably, in a change in editorial policy which is reflected in the contents of Volume 8. There has been a marked de-emphasis on the inclusion of organic parent compounds followed by an exhaustive and voluminous cataloging of azide, azido, azo, diazido, diazonium, diazo, nitro, dinitro, polynitro, hitr amine, nitrate (esters and salts), dinitrate, poly nitrate, nitroso, polynitroso, chlorate, perchlorate, peroxide, picrate, etc, derivatives — regardless of whether any of these derivatives exhibit documented explosive or energetic properties. Only those materials having such properties have been included in this volume... 

At best, expl power i a somewhat nebulous quantity. If we consider relative power as measured in a Ballistic Mortar or Trauzl Block, then OB correlates reasonably well with relative power, provided these comparisons are made for similar expls. This is illustrated in Fig 1, where Ballistic Mortar measurements axe respectively correlated with OB for nitro, nitramine, nitrate ester and aluminized expls. In general Ballistic Mortar measurements are more reproducible than Trauzl Block data. Consequently we have shown these in preference to Trauzl Block measurements. Correlation between Trauzl block data and OB are reported in Refs 1 8... 

A group of flavoenzyme reductases mediate the reduction both nitrate esters and C= C double bonds generally activated with carbonyl or nitro functions. The structures of the substrates vary widely (references in Faber 1997). 

Uncertainty factor 3 no unusually susceptible populations were identified and the end point was a threshold effect. More severe headaches are known to occur in some patients medicated with other nitrate esters and the threshold for vasodilatation in the key study did not vary greatly among individuals. 

Yinon, J. Mass Spectrometry of Explosives Nitro Compounds, Nitrate Esters, and Nitramines. Mass Spectrom. Rev. 

The most important color reaction for nitrate esters and nitramines is based on the formation of nitrite ions (NO2 ), upon reaction of these compounds with alkahs [31,32]. The nitrite ions are then detected by the classical Griess reaction [5,6]. 

Several pathways are known to take place in the reaction between nitrate esters and alkalis. The mechanism that leads to the formation of nitrite ions is an (X-ehmination abstraction of an CC-hydrogen atom, with the conversion of the nitrate ester to nitrite ion and the corresponding carbonyl compound [31] (Eq. (4)) ... 

Alkahne hydrolysis, followed hy the use of sulfanihc acid and 1-naphtylamine, was the basis of a spot test for NG [37], as well as for several nitrate esters and nitramines, including NG, NC, tetryl, and RDX [38]. It is also a common spray for the detection of nitrate esters and nitramines on TLC plates [25, 29, 37, 39—41]. 

The DPA test is another common spot test for nitrate esters and nitramines [1, 3, 4, 50-55]. The reagent (1% DPA in concentrated sulfuric acid) is oxidized in the presence of these explosives, producing a deep blue color. 

A solution of the alkaloid brucine in concentrated sulfuric acid was reported [4, 38, 50] to give orange-red colors with nitrate esters and nitramines, probably by oxidation ofbmcine. 

A field test for the detection of TNT in contaminated soils (e.g., near ammunition plants) was based on the color reaction between TNT and alkalis (the Janowski reaction [7]) [26]. A few milligrams of the suspected soil are placed on filter paper and sprayed with 1 M NaOH acetone (1 1). A red color indicates the possible presence of TNT. Detection limits were reported to be 2-50 mg of TNT per 1 kg of soil, depending on the type of soil. The same group [55] used the oxidation of DPA in concentrated H2SO4 as the basis of a field test for nitrate esters and nitramines in soil. 

An extremely mild method for the synthesis of nitrate esters from easily oxidized or acid-sensitive alcohols involves the decomposition of a nitratocarbonate (29). The nitratocar-bonate is prepared in situ from metathesis between a chloroformate (reaction between phosgene and an alcohol) and silver nitrate in acetonitrile in the presence of pyridine at room temperature. Under these conditions the nitratocarbonate readily decomposes to yield the corresponding nitrate ester and carbon dioxide. Few examples of these reactions are available in the literature and they are limited to a laboratory scale. 

Treatment of primary nitramines with absolute nitric acid yields the corresponding nitrate ester and nitrous oxide. 

Acyl nitrates react with low molecular weight aliphatic alcohols to give the alkyl nitrate ester and the corresponding carboxylic acid. " ... 

Despite the moderate to good yields obtained for a range of primary and secondary nitramines, the above methods have not found wide use. Their use in organic synthesis is severely limited by the incompatibility of many functional groups in the presence of strong bases. This is particularly relevant to the synthesis of explosive materials, where nitrate ester and C-nitro functionality are incompatible with strong bases. 

Fifer, R. L., Chemistry of Nitrate Ester and Nitramine Propellants, Fundamentals of Solid-Propellant Combustion (Eds. Kuo, K. K., and Summerfield, M.), Progress in Astronautics and Aeronautics, Vol. 90, Chapter 4, AIAA, New York, 1984. 

CA 41, 1842(1947) (Plastic explosives consisting of a liquid nitrate ester and a 1 3 mixture of sol insol Nitrocelluloses)... 

S.L. (1992) Energetic composites of cyclodextrin nitrate esters and nitrate ester plasticizers, US Patent 5,114,506. 

Nitroxyethyl Nitramine Plasticizers Nitroxy ethyl nitramine (NENA) plasticizers are a new family of energetic plasticizers which have emerged recently. These are effective plasticizers in energetic formulations, particularly in nitrocellulosic systems. NENAs contain both nitrate ester and nitramine functionalities and possess the general structure RN (N02).CH2.CH2.0N02 where R is methyl, ethyl, propyl, isopropyl, butyl and pentyl. 

Nitrate Ester Plasticizers As discussed in Section 2.2.4 of Chapter 2, nitroglycerine (NG) is a high performance nitrate ester and is considered the first energetic plasticizer for commercial explosives. 

According to Ref 10a, Hydrazoic acid molecules are linked into an infinite zigzag chain by N—H... N hydrogen bonds. Thus its high value of specific heat of vaporization is not unexpected. A fairly reliable Trouton constant of 23.5 eu for hydrazoic acid also suggests a non-ideal associated liquid. The other three azides in Table 8 have specific heats of vaporization similar to those of nitrate esters and nitramines... 

Scission of alkoxy radicals (12) generated from nitrate esters and BU3S11H furnish a-amino acid radicals (13) (Scheme 4). This new method for forming a-amino acid radicals may be useful for generating site-specific radicals in peptides.25 The reactions of C(2) glyceryl radicals (14) have been observed by EPR. Whereas the phosphate derived radical (14a) gave the reduced product (15a) in 70% yield, the unsubstituted... 

---