S-Trinitrobenzene

Current views (100) on the mechanism of bromination by NBS invoke the formation of molecular bromine and bromine atoms in low concentration, which subsequently act as the brominating agent. The bromination reaction was studied in detail in this laboratory under a variety of conditions using 93 (R = Ms) as a model. The product 94 (R = Ms) was indeed formed (42%) when NBS was substituted by 1.1 equivalents of bromine which was added at a slow rate to the reaction mixture. The yield was 68% when benzoyl peroxide was used as a catalyst. Using NBS alone or in the presence of reagents such as barium carbonate, pyridine, or s-trinitrobenzene, the yield was 60-70%. 

The flash photolysis of s-trinitrobenzene (TNB) aerated solns in alcohols generated a transient species with absorption maxima at 430 and 51 Onm (Ref 27). The yield of the transient was a function of oxygen concn, and its rate of formation was viscosity dependent. In deaerated solns, instead of the transient, a brown permanent product, identified as a charge transfer... 

Ferrocene, cobaltocene, and nickelocene, react with iodine (as well as with s-trinitrobenzene or picric acid 341) to form ionic species ... 

Capellos C, Suryanarayanan K. 1973. Flash photolysis of s-trinitrobenzene solutions. Int J Chem Kinetics 5 305-320. 

F.B. Wells, S-Trinitrobenzene as a Binder in Compression-Molded Explosive Compositions , PATR 4783 (1975) [It was found that the ideal HMX/TNB ratios required to provide compression-molded pellets that come close to the theoretical max d are 95/5 to 94/6 with no TNB loss at SOOOpsi compression press. It was also noted that the HMX used need not be of a very fine particle size to be successfully molded in the mixt] 54) J.R. Hendrickson F.B. Wells, Castable Composite Explosive Compositions Containing a Mixture of Trinitrobenzene (TNB) and Trinitroxylene , USP 3994756 (1976) CA 86, 75497 (1977) [A castable composite expl which meets Mil Specs is claimed which contains TNB 26.25, Trinitroxylene 3.75, and HMX 70 wt %] 55) F.B. Wells, High-... 

Phthalic anhydride Nitrobenzene 2,6-dini trotoluene Maleic anhydride m-dinitrobenzene s-trinitrobenzene... 

The largest group of organic molecular compounds, in which hydrogen bond formation plays no part, are the compounds, usually in the ratio 1 1, between on the one hand aliphatic and aromatic nitro compounds (nitromethane, tetranitro-methane, chloropicrin CC13N02, nitrobenzene, s-trinitrobenzene, picric acid), quinones, anhydrides (phthalic acid-and maleic acid anhydride) and ketones with on the other hand especially aliphatic and aromatic amines (aniline, pyridine), unsaturated aliphatic and aromatic hydrocarbons, ethers etc. 

A similar, but probably nucleophilic substitution was studied by Lobry de Bruin and van Leent [134]. By acting with hydrochloride at 2S0°C they re-Piced nitro groups in dinitrobenzenes and s-trinitrobenzene to obtain dichloro-lltnzenes and s-trichlorobenzene respectively. 

This was described by a number of authors (Vol. 1) for example, Powell and Muse, Rapson, Saunder and Stewart and Wallwork [95] subjected a few complexes of s-trinitrobenzene to X-ray analysis. Wallwork concluded that the structure can be summarized and plane-to-plane packing of the components. The relative dispositions of the components are such as to allow the maximum degree of overlap between their molecular ir-orbitals. Figure 12 gives a diagrammatic presentation of the complexes of sym-trinitrobenzene with naphthalene, and Fig. 13 - with anthracene [96]. 

The NH4Y zeolite was prepared from the Linde NaY zeolite by treatment with ammonium nitrate solution to give a 74% exchange product. The dried material so produced was evacuated at the desired temperature of pretreatment overnight and cooled in an evacuated sample tube sealed off with a break-off seal. Three-tenths ml of a 2.1-milf benzene solution of l,3,S-trinitrobenzene (TNB) was degassed by repeated freeze-pump-thaw cycles and contacted with the zeolite through the break-off seal. The ESR measurements were made at room temperature. 

Figure 4.14 Energy for the maximum absorbance for charge transfer complexes of s-trinitrobenzene, tetracyanoethylene, and chloranil with various donors plotted against the adiabatic ionization potential of the donor. Recent ionization potentials from the NIST tables were used. The vertical displacement results from the differences in the Ea of the molecules. The calculated curves were obtained by using a two-parameter nonlinear least squares. The values of the constants are given in Table 4.5, where they are compared with published values. Data from [8, 30, 32].

Figure 4.15 Electron affinities of charge transfer complex acceptors calculated from C2 = 2.9 versus the current best adiabatic electron affinities. This is a precision and accuracy plot. The zero intercept slope indicates that the same quantities are measured. The compounds are maleic anhydride, tetrachlorophthalic anhydride, benzoquinone, trinitro-flourenone, s-trinitrobenzene, chloranil, tetracyanoquinodimethane, and tetracyanoethylene in order of their electron affinities.

To determine by spectrophotometric measurements the dissociation constant m carbon tetrachloride of the molecular complex formed between acenapthene and s-trinitrobenzene. 

S Trinitrobenzene add. comp, yellow needles from MeOH. M.p. 165-5°. 

Compound s-Trinitrobenzene Aoenaphthene m-Dinitrobenzene Acenaphthene Nitrobenzene Aoenaphthene... 

Binding energy of the molecular association of s-trinitrobenzene in Cal. Binding enemy of the molecular aasociations of anthracene in Cal. ... 

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