Addition compounds trinitrobenzene

The selenium-dehydrogenation products of isorubijervine have not yet been fully examined, but the two structurally significant products, 5-methyl-2-ethylpyridine and a hydrocarbon, C17H14, m.p. 135-6°, yielding a picrate, m.p. 134-5° and a 1 3 5-trinitrobenzene addition compound, m.p. 165-6°, which identify it as 1 2-ci/cZopentenophenanthrene, indicate for worubijervine, as for rubijervine, a normal sterol structure, for the non-nitrogenous portion of the molecule. ... 

Reactions specific to sym-trinitrobenzene Addition compounds Preparation of sym-trinitrobenzene Direct nitration of m-dinitrobenzene Preparation from a-trinitrotoluenc Preparation from picryl chloride Preparation from benzyl chloride Preparation from m-xylene Other preparatory reactions... 

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. 

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... 

Trimethylacetic acid, 350, 351 Trimethylamine hydrochloride, 414,416 Trimethylene dibromide, 279 Trimethylene dicyanide, 407, 409 Trimethylene-di-iodide, 288 1 3 5-Trinitrobenzene, 965 addition compounds of, 519 ... 

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. 

Ross and Labes [134] determined the heats of formation of the addition compounds 1,3,5-trinitrobenzene-naphthalene and -aniline, and found them to be 3.3 and 5.1 kcal/mole respectively. 

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]). 

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. 

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. 

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. 

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 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. 

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