1.3.5- Trinitrobenzene addition compounds with

Complexes in Which the Acceptor Is an Organic Molecule. Picric acid, 1,3,5-trinitrobenzene, and similar polynitro compounds are the most important of these. Picric acid forms addition compounds with many aromatic hydro... 

The carbon skeleton of samandarine was elucidated by selenium dehydrogenation of samandiole (Vila) at 320°-340°. This reaction (7) yields an oily mixture of hydrocarbons which was separated by means of addition compounds with trinitrobenzene and with trinitrofluorenone. The main product was a crystalline hydrocarbon, C15H16, which proved to be l,2-dimethyl-5,6-cyclopentenonaphthalene (XI). 

Trinitrobenzene is also but little used. It forms additive compounds with amines and with naphthalene. It gives an intense red colour with alicalta in presence of alcohol. 

The decomposition of some addition compounds of aromatic hydrocarbons (formed with picric acid, styphnic acid or trinitrobenzene) on an adsorbent column has been made use of for the preparation of pure hydrocarbons for spectral analysis. For example, chamazulene trinitrobenzene addition compound decomposes on alumina column. The pure hydrocarbon released is eluted with petroleum ether, leaving behind trinitrobenzene (which has high affinity for alumina) in the upper part of the column. This again can be eluted with more polar solvents. 

The ability to form addition compounds, especially with aromatic hydrocarbons composed of condensed rings, is one of the specific properties of aromatic poly-nitro compounds. For example, compounds of trinitrobenzene or picric acid with naphthalene, as well as with other hydrocarbons with condensed rings, are very characteristic. Generally they are intensely coloured. 

It has also been suggested that 1,3,5-trinitrobenzene and m- dinitrobenzene may react with amines to form addition compounds by a proton transfer reaction (Lewis and Seaborg [136], Farr, Bard, and Wheland [137]). 

It is important to add that some molecular addition compounds of sym- trinitrobenzene with hydrocarbons can serve for identification and purification of hydrocarbons (Veibel [141]). Trinitrofluorenone seems to be of particular value (Orchin and Woolfolk [142], Lepley [154]). 

Addition compounds. sym-Trinitrobenzcne readily forms well defined, often coloured compounds with hydrocarbons with condensed rings. Kremann and co-workers [18,44], Jefremov and co-workers [9,11,44a], Sudborough and Beard [44b] and their co-workers have studied most of these systems, containing sym-trinitrobenzene, by thermal analysis. 

Addition of nucleophiles to aromatic compounds with several nitro or cyano groups leads to the formation of a resonance-stabilized carbanion known as a Jackson-Meisenheimer complex. For example, addition of sulfite ion to 1,3,5-trinitrobenzene leads to the complex 4 (Figure 3.5). 

The reaction of l,3,S-trinitroben2ene with diazomethane was carried out as early as 1898-1900 [88, 89), but only recently de Boer rationalized it as a nucleophilic addition leading to seven member ring condensed with two cyclopropane rings when the molar ratio of trinitrobenzene to diazomethane was 1 3. The first step of the reaction was a type of Jackson-Meisenheimer complex (Ai) and the final product was trismethylene-trinitrobenzene (A ) [90—92a] (19). The reaction is temperature dependent at —80 C compound (A ) was formed. 

EDS applications. In addition, new test data from the ACWA Program indicate that polynitroaromatic compounds (e.g., trinitrobenzoic acid and trinitrobenzene) precipitate during treatment of liquid wastes containing explosive residues, which may be present in EDS neutralents (Winkler, 2001). Electrochemical oxidation with Ce(IV) is also dropped from track two, owing to its relative immaturity and the possibility of corrosion and plugging of the electrochemical cells as a result of higher levels of metal ions in the EDS neutralents. 

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