1,3,5-Tris 2,4,6-trinitrobenzene

A synthesis of hexanitrobenzene (55) has been reported which involves hydroxyamino oxidation. Although no experimental details of this procedure are given the synthesis is reported to start from partial reduction of 1,3,5-trinitrobenzene (2) to l,3,5-tris(hydroxyamino)benzene... 

Tris(picrylamino)-l,3,5-trinitrobenzene (113), the product from condensing three equivalents of aniline with 1,3,5-trichloro-2,4,6-trinitrobenzene followed by nitration with mixed acid, is a high-molecular weight explosive which shows good thermal stability (m.p. 234 °C) but is readily detonated. " ... 

Similar routes have been used for the synthesis of other polynitrophenylenes. 1,3,5-Tris(2,4,6-trinitrophenyl)-2,4,6-trinitrobenzene (160) is synthesized from the reaction of 1,3,5-trichloro-2,4,6-trinitrobenzene with three equivalents of picryl chloride in the presence of activated copper powder in refluxing mesitylene. " 2,2",4,4, 4",6,6, 6"-Octanitro-m-terphenyl (161) has been synthesized from picryl chloride and l,3-dichloro-4,6-dinitrobenzene. ... 

Beilstein Kuhlberg investigated nitration of toluene with mixed nitric-sulfuric acid of various concns and isolated for the first time several isomers of mono- and dinitro-toluene. They also prepd in 1870 TNT, but did not prepare Trinitrobenzene. At about the same time, mono-, di-, tri- and tetra-nitronaphthalenes were prepd (Ref 12, p 18). Trinitrobenzenes were prepd in 1882 by P. Hepp... 

Ethy 1-2,4,6-tri nitrobenzene or 2,4,6-Trinitro-1-ethylbenzene (TNEtB) listed in some papers as 2-Ethy 1-1,3,5-trinitrobenzene,... 

DNB — Dinitrobenzene DNCB — Dinitrochlorobenzene DNCr — Dinitiocresole DNPh — Dinitro-phenol DNT — 2,4, Dinitrotoluene EtN — Erythritol Tetranitrate HNDPhA — Hexanitio-diphenylamine MHeN — Mannitol Hexanitrace MNPh — Mononitrophenol MNT — Mononitrotoluene PA — Picric Acid PETN — Pentaerythritol Tetranitrate TNAn — Trinitroaniline TNAns — Tri-nitroanisole TNB — Trinitrobenzene TNCr — Trinitrocresole TNPh — Tri nitro phenol TNT —... 

Figure 2.1 Structures of mono, di and tri amino derivatives of trinitrobenzene(TNB).

A number of explosives for various applications have been synthesized, characterized for structural aspects, thermal and explosive properties by us in India and are being evaluated [193-198] for their intended end-use. The evaluation of BTATNB [Structure (2.27)] indicates that it is slightly more thermally stable than PATO [Structure (2.24)] coupled with better insensitivity toward impact and friction [71]. The data on thermal and explosive properties of some aromatic nitrate esters suggest that l,3,5-tris(2-nitroxyethyl nitramino)-2,4,6-trinitrobenzene [Structure (2.54)] is a potential substitute of PETN [193]. An explosive called 2,4,6-tris (3,5 -diamino-2, 4, 6 -trinitrophenylamino)-l,3,5-triazene [designated as PL-1 Structure (2.55)] is a new thermally stable and insensitive explosive which on comparison with TATB suggests that it is slightly inferior to TATB [Structure... 

M,N -Dimethy 1-2,4,6-trinitro-N,N dinitro-phenylenedi amine N N -Bistmethyl) -N,N -d initramino-2,4,6-tri nitrobenzene 1,3-Bis(methylnitramino)-2,4,6 trinitrobenzene or N,Ni-Dimethyl-H,N,2,4,6-pentanitropHenyl-ene-1,3-diamine called by the British Ditetryl. This must not be confused with American Ditetryl, called.hy the British Octyl, which is l,2-Bis(2(4,6,-trinitro-anilino)-ethane (See Vo I 2 of Encycl, p... 

That is the reason why the performance of picric acid (trinitrophenol) is only vary slightly higher than that of trinitrobenzene and why the performance of tri-nitroanisole is much the same as that of trinitrotoluene. 

Three isomers of trinitrobenzene are known 1,3,5-trinitrobenzene (sym-tri-nitrobenzene), 1,2,4-trinitrobenzene and 1,2,3-trinitrobenzene ... 

Wyatt and Brayford [79] have tried to explain the inconsistency of the spectro-graphic and cryometric results. On the basis of their cryometric measurements on solutions of 2,4,6-trinitrotoluene, 1,3,5-trinitrobenzene and picric acid in sulphuric acid in the presence of compounds interfening with the dissociation of the solvent, they finally concluded, on the basis of the spectrophotometric measurements, that polynitro compounds should be regarded as non-electrolytes. 

It is obvious here to think of an interaction of the Debye type of the appreciable moment of the nitro or carbonyl group with the readily polarizable unsaturated C — C bond in the unsaturated hydrocarbons or with the likewise readily polarizable free electron pair in the amines, etc. Actually the stability increases with increasing polarizability, compare for example, the heat of formation of j-trinitrobenzene with, respectively, benzene, naphthalene and anthracene AH 0.6, 3.4 and 4.4 kcal. In the series mono-, di- and tri-nitro-benzene with acenaphthene AH also increases with increasing number of partial moments, namely AH — o, 1.35 and 2.45 kcal. Nevertheless this explanation is inadequate, nitromethane with a moment [x = 3.54 D gives very much less stable compounds than nitrobenzene with (X = 4,22 D, while nitrosobenzene with [x =3.2 D gives stronger colour effects than nitrobenzene. 

When supramolecular polymers are treated with bulky stopper groups, they may form poly[2]rotaxane daisy chains [32,60-68]. Cyclic tri[2]rotaxanes (daisy chain necklace) containing cyclodextrins have been prepared from the mixture of 6-(4-aminocinnamoyl)-Q -CD and 2,4,6-trinitrobenzene sulfonic acid sodium salt [50,59] in an agueous solution (Fig. 21). If the molecule changes its conformation (or co-conformation), the ring may expand or shrink by external conditions (temperature, solvents, photochemically, elec-trochemically). These compounds are important because the cycle can be used as a chemical valve as seen in ion channels in biological membranes. 

A few more papers should be mentioned as regards electronic spectra of aromatic nitro compounds nitrobenzene, dinitrobenzene and trinitrobenzene [20] and the work of Barth [21 ] who subjected mono-, di- and tri-nitrobenzenes and toluenes to detailed spectrophotometric ultraviolet-visible studies and developed a quantitative analysis of TNT in the presence of cyclonite, octogene and waxes. 

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