Addition compounds trinitrotoluene

According to Yefremov and Khaibashev [35], Giua [36], C. A. Taylor and Rinkenbach [37], tetryl and trinitrotoluene form an additive compound in the ratio of one mole of tetryl to two moles of trinitrotoluene which readily dissociates and melts at 6I.1°C (Taylor and Rinkenbach report m.p. of the addition compound as 68°C). 

It also forms molecular addition compounds with a-trinitrotoluene and 2,4,6-tri-nitroanisole (T. Urbadski [6, 7]). 

Although successfully carried out with model compounds, the cyclopentyl i dene acetal here could not be hydrolyzed selectively in the presence of the other protecting groups. Selective deprotection occurred only upon addition of trinitrotoluene, which us a more electron-deficient aromalic system forms a charge-transfer complex with the electron rich aromalic portion of the PMPh acetal. The charge-transfer complex decreases the electron density of the acetal and thus increases its stability, presumably due to reduced stabilization of cation 38 In this way it proved possible to release the alcohol functions at C-12 and C-13 selectively with acid. 

A detailed list of addition compounds formed by sym- trinitrobenzene, 2,4,6-trinitrotoluene, picric acid and other polynitro compounds is given in the appropriate paragraphs devoted to these nitro compounds. 

According to T. Urbaliski [log], a- trinitrotoluene forms with erythritol tetra-nitrate an unstable addition compound, (4 1), melting at about 65°C. 

This was determined by diluting the solution to hydrolyse the addition compounds. Precipitation of recovered a- trinitrotoluene gives the transient solubility (S3). By definition S2 = SrS3. 

Trinitro-m-xylene forms addition products less easily than a- trinitrotoluene. Undoubtedly the two methyl groups present in the ring reduce its ability to form addition compounds. 

Beta and gamma trinitrotoluenes react with aniline, but the product formed is not an additive compound... 

Anthracene reacts with all of the trinitrotoluenes similarly to naphthalene, addition compounds being formed. 

Sudborough (8) has succeeded in forming addition compounds with alpha and beta naphthylamine and alpha trinitrotoluene. These reactions take place at moderate temperatures in alcoholic solutions. 

The systematic studies of T. Urbanski, Kwiatkowski and Miladowski [76] proved that the addition of an aromatic nitro compound distinctly enhances the stability of nitrocellulose and nitrocellulose powder. Thus, nitrocellulose containing 13.4% N which on heating for 5 hr at 120°C had pH=2.28 showed pH=2.89 on addition of 9 1% p-nitrotoluene, pH=3.17 on addition of 9.1 % 2,4-dinitrotoluene and pH=3.34 on addition of the same amount of a-trinitrotoluene. The same samples when heated in a constant volume (Tagliani test) gave at 134.5°C a pressure of decomposition... 

From a practical point of view, reduction of NACs is of great interest for two reasons. First, the amino compounds formed may exhibit a considerable (eco)toxi-city, and therefore may be of even greater concern as compared to the parent compounds. Additionally, the reduced products may react further with natural matrices, in particular with natural organic matter, thus leading to bound residues (see sections on oxidations below). One prominent example involves the reduction products of the explosive, 2,4,6-trinitrotoluene (TNT see Fig. 14.6), particularly the two isomeric diaminonitrotoluenes (2,4-DA-6-NT and 2,6-DA-4-NT) and the completely reduced triaminotoluene (TAT). These have been found to bind irreversibly to organic matter constituents present in soils (Achtnich et al., 2000) and sediments (Elovitz and Weber, 1999). This process offers interesting perspectives for the treatment of NAC contaminated sites. In fact, a dual step anaerobic/aerobic soil slurry treatment process has been developed for remediation of TNT contaminated soils (Lenke et al., 2000). 

It has been established experimentally (T. Urbanski, Kwiatkowski, Miladowski [22]) that the addition to pentaerythritol tetranitrate of such nitro compounds as nitrobenzene, nitrotoluene, dinitrobenzene, dinitrotoluene, trinitrobenzene, and trinitrotoluene, decreases its stability as determined by heating to 120-135°C. The degree of decomposition of PETN, heated alone or in mixtures, can be estimated in terms of the pH-values determining the acidity of the decomposition products (Table 32, Fig. 72). 

The selective nucleophilic displacement of one ortho nitro group from 2,4,6-trinitrotoluene by esters of mercap-toacetic acid followed by oxidation leads to 2-(alkoxycarbonyl)methylsulfonyl compounds. These sulfones react with aromatic aldehydes under Knoevenagel conditions to produce thiochroman 1,1-dioxides 477, probably via a stilbene and a subsequent intramolecular Michael addition. Activating groups other than nitro are compatible with the route (Scheme 167) <2003RJ0397>. 

Tertiary nitro compounds, of course, do not undergo tautomeric transformation, and they might be expected to be resistant to alkalis. Nevertheless aromatic nitro compounds, and polynitro-ones in particular, are very sensitive to alkalis, and undergo transformation when treated with them. For example, sym-trinitrobcnzcnc and also a- trinitrotoluene, when reacted with potassium hydroxide in methyl alcohol solution, form dark addition products (see also p. 202). Under certain conditions the nitro group can break off to form high molecular compounds. 

Nitro compounds, particularly the higher nitrated derivatives, readily enter into nucleophilic reactions. The reactions of aromatic halogenonitro compounds with bases (p. 453), as well as the addition of potassium methoxylate on to sym-trini-trobenzene resulting in the formation of an anisole derivative will be discussed below. Similar addition reactions of potassium methoxylate to trinitrotoluene (p. 301) and trinitroanisole (p. 546) are also known. These reactions were described in detail by Meisenheimer [36-38], Confirmation of such an interpretation of the reaction is provided by the fact that in the reaction of potassium ethoxylate with trinitroanisole the same dark coloured product (I) is obtained, as when potassium methoxylate is reacted with trinitrophenetole ... 

Of all nitro derivatives of toluene, trinitrotoluene is the most important as an explosive. It is by the most often used high explosive among those derived from aromatic compounds. It is popular because it is simple and relatively safe to manufacture, Mid has high explosive power, and above all because its high chemical stability and low sensitiveness to impact and friction make it safe to handle. In addition, its toxicity is low and thus it compares favourably in this respect with the nitro derivatives of benzene. 

Other compounds such as 2,4-dinitrotoluene, 2,4,6-trinitro-m-xylene, 2,4,5-trinitrotoluene, hexogen, only slightly decreased the rate of crystallization (e.g. the addition of 1 mole % of 2,4-dinitrotoluene and hexogen caused a decrease in rate of crystallization of TNT at 74°C from 2.5 cm/min to 1.89 and 1.78 cm/min respectively). 

Figure 72 shows the influence of trinitrotoluene on the rate of nitration of dinitrotoluene in heterogeneous systems at 90°C. It is interesting to note that the addition of 66-70% of trinitrotoluene to dinitrotoluene more than halves the rate of the nitration, Further increase in the content of trinitrotoluene promotes nitration of dinitrotoluene. When the content of trinitro compound reaches 91% the yield of trinitration is almost the same as that of the pure dinitrotoluene. 

Brady, Hewetson and Klein [139] tried to elucidate the mechanism of the reaction of sulphitation of unsymmetrical trinitrotoluenes. They assumed the formation of an addition product of sodium sulphite and the nitro compound in the first stage. 

Alkalies produce addition, substitution, and condensation products. Alkalies and alkali compounds produce red colorations with alpha trinitrotoluene. Coparisow found that when 5 c.c. of a saturated solution of potassium hydroxide in methyl alcohol, cooled in solid carbon-dioxide-ether mixture, are added to. 166 g. of pure symmetrical trinitrotoluene, dissolved in a mixture of 1 c.c. pryidine and, 5 c.c. methyl alcohol the latter solution being kept cool in solid carbon-dioxide-ether mixture, the color change took place at a temperature as low as —65° C. 

Although many other explosives and explosives-related compounds exist, only the data for 2,4,6-trinitrotoluene (TNT) and its breakdown products, the cyclic nit-ramines (RDX and HMX), tetryl, trinitrobenzene, and nitroglycerin will be reviewed in this chapter. Two dinitrotoluene isomers are also included, as they are still used as explosives in addition to being side-products of TNT synthesis. 

You have to determine (a) formaldehyde and acetaldehyde in 50 samples of white wine per day (b) 2,4,6-trinitrotoluene in white powder samples which might be potential material in making bombs—3 to 5 samples per month (c) copper content in a rare Etruscan vase (d) a toxic keto compound in an antibiotic, the analysis being done in a production-line quality-control laboratory in a pharmaceutical company. In which cases and why would you use a standard-addition method and when would you use a calibration curve for evaluating current-versus-voltage curves ... 

An initial photolysis reaction can result in the generation of reactive intermediates that participate in chain reactions that lead to the destruction of a compound. One of the most important reactive intermediates is the hydroxyl radical, HO-. In some cases, sensitizers are added to the reaction mixture to absorb radiation and generate reactive species that destroy wastes. Hazardous waste substances other than 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) that have been destroyed by photolysis are herbicides (atrazine) 2,4,6-trinitrotoluene (TNT) and polychlorinated biphenyls (PCBs). The addition of a chemical oxidant, such as potassium peroxydisulfate, K2S20g, enhances destruction by oxidizing active photolytic products. 

Found in m-dinitro compounds examined where other additional groups, if any, were ortho to the nitro. Not found in sym-trinitro compounds but present in 2,3,4- and 2,4,5-trinitrotoluene. Absent in 3,5-dinitrobenzoic acid and 4,6-dinitro-o-cresol. It appears that a group meta to the nitro inhibits the band. 

---