1.3.5- TRI NITROBENZENE

The exclusive formation of the C-1 adduct between 2,4,6-trinitroanisole and n-butylamine has actually been detected, as a transient intermediate en route to AT-(n-butyl)picramide, by a low-temperature flow n.m.r. experiment. Further kinetic data for the reversible reaction between the 1,3,5-tri-nitrobenzene-methoxide cr-complex and aniline in DMSO-MeOH solutions, yielding the 1,3,5-trinitrobenzene-anilide dissociative mechanism involving rate-determining interconversion of free TNB and the protonated anilide complex. The failure of aromatic primary amines by themselves to form stable (7-complexes with TNB is due to an unfavourable overall equilibrium represented by equation (3), while the additional presence of the strong base... 

Tri methy 1-2,4,6-tri nitrobenzene Trinitroacetic acid Trinitroacetonitrile Trinitroamine cobalt... 

In aliphatic amines (diethylamine or triethylamine) the intramolecular hydrogen abstraction is quenched almost completely. Instead, smooth photoreduction of the nitro group without participation of the side chain is observed with 1,3,5-tri-fezf-butyl-2-nitrobenzene (5) and 14, R = C(CH3)3 ). Products derived from the respective phenylhydroxylamines were isolated in both cases. Again, an electron transfer, which does not seem to suffer from steric restrictions, is operative (see also Section A. 1.3). 

This reaction was first reported by Baddeley in 1930s. It is the migration of alkyl groups in polyalkylbenzenes or polynuclear aromatic compounds in the presence of anhydrous aluminum chloride or the mixture of protonic acid and Lewis acid. In one of Badde-ley s experiments, when 1,3,4-tri-n-propylbenzene was warmed with AICI3 at 100°C, the 1,3,5-tri-n-propyl was formed, along with the lower and higher alkylated benzenes. After extensive studies, it was found that the amount of a-isomer can be reduced by the addition to the reaction mixture of a variety of substances (e.g., nitrobenzene and excess acid chloride) that complex strongly with aluminum chloride. Likewise, less a-isomer has been observed when this reaction is carried out in nitrobenzene. In addition, isomerization of hindered aromatic ketones occurs if the ketones are melted with an excess amount of aluminum chloride and sodium chloride. ... 

It has been shown by studies of kinetic isotope effects that the deprotonation step is fast and does not influence the rate of nitration. The cases in which this has been demonstrated include, among others, nitration of benzene, toluene, nitrobenzene, and bromobenzene in nitric acid-sulfuric acid nitration of benzene, toluene, and fluorobenzene with nitronium tetrafluoroborate and nitration of toluene in nitric acid-nitromethane. The only exception, where primary isotope effects are observed, is in the case of substituted 1,3,5-tri-r-butylbenzenes. Here, steric hindrance to deprotonation is apparently sufficiently large to make deprotonation slow relative to the first two steps in the nitration mechanism. 

To a solution of 16.22 g (100 mmol) of 1,3,5-tris-hydroxybenzene (Aldrich Chemical Co.) and 44.59 g (316 mmol) of l-fluoro-4-nitrobenzene (Aldrich Chemical Co.) in a mixture of 100 mL V,V-methylacetamide (DMAc) and 100 mL toluene, 44.2 g (320 mmol) of potassium carbonate was added. The mixture was heated to gentle reflux with a Dean-Stark apparatus and mechanically stirred for 24 hours. At the end of the reaction, a mixture of 100 mL methanol and 100 mL of water was added with stirring. The reaction mbcture was chilled and the crystallized product filtered, washed with 1000 mL of water, followed by 300 mL of methanol. The product was redissolved in ethyl acetate, decolorized... 

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,... 

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

The search for cis-trans isomerism in other systems such as the reaction of 1,3,5-trinitrobenzene with alkoxide ions (8) or hydroxide ion (8), and the reaction of l-X-2,4,6-tri-nitrobenzene with sulfite ion where X = OMe, 0", NH2, NHMe,... 

Chloro-3, 5-dimethoxy-2,4,6-tri nitrobenzene or 5 -Chi oro-2,4,6-trinitroresorci nol Di methyl ether... 

More elaborate catalysts have also been used, like tris(3,6-dioxaheptyl)amine (TDA-1) in dechlorinations of chloropyridines by benzyl alcohol160 and of 4-chloronitrobenzene, 4-chlorobenzonitrile, and 2-chloro-5-(trifluoromethyl)nitrobenzene by phenols and methanethiol.161... 

Diazonium salt solutions that have been obtained from weakly basic amines in concentrated H2S04 with nitrosylsulfuric acid and 85 % phosphoric acid give good yields of the derived aryl iodides when treated with cold aqueous KI for example, the preparation of 1,2,3-triiodo-5-nitrobenzene from 2,6-diiodo-4-nitroaniline is described in detail in Organic Syntheses 1223 and m-iodonitrobenzene, l,2-diiodo-4-nitrobenzene, l,4-diiodo-2-nitrobenzene, and 1,2,4-tri-iodo-3-nitrobenzene have been obtained analogously.1224... 

FIGURE 1 Influence of the solvent s basicity on the rate of thermal dehydrichloiination in solution 1 - n-dichlorobenzene, 2 - o-dichlorobenzene, 3 - naphthalene, 4 - nitrobenzene, 5 - acetophenone, 6 - benzonitrile, 7 - di-M-(chlorophenyl-chloropropyl) phosphate, 8 -triphenylphosphite, 9 - phenyl-fv 5-(P-chloroethyl) phosphate, 10 - tri-( -chlorophenyl phosphate), 11 -2-ehtyUiexylphenyl phosphate, 12-tricresyl phosphate, 13-cyclohexanone, 14 - phenyl-fa 5-(P-chloropropyl) phosphate, 15 - tri-P-chloroethyl phosphate, 16 - tri-P-chloropropy 1 phosphate, 17 - di-2-(ethy Uiexyl) phosphate, 18 - 2-ethyUiexylnonyl phosphate, 19 - tri-(2-ethylhexyl) phosphate, 20 - tributyl phosphate, 21, 25 - dibutyl phthalate, 22, 26 - di-2-ethylhexyl adipinate, 23, 27 - dioctyl phthalate, 24, 28 - dibutyl sebacinate. Concentration of PVC in solution 1-24 - 0.2 wt.%, 25 - 28 - 2wt.% 423 K, under nitrogen. 

Preparation by heating a mixture of 4-hydroxybenzoic acid and hydroquinone in OH nitrobenzene in the presence of boron triflu oride at 80° for 30 min (64%) [186]. N.B. In the patent, this compound was erroneously called 3, 4,5 -tri-hydroxybenzophenone (assay 5, table page 3) [186]. Preparation by Friedel-Crafts acylation of hydroquinone dimethyl ether with p-anisoyl chloride (AICI3/CS2/ 3 h at r.t.), followed by demethylation (AICI3/ Toluene/1 h at 120°) (65%). -Refer to Chem. Abstr., 44, 1271f (1950)L... 

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