2-Nitro-mesitylene

Nitro-mesitylene (2-Nitro-1,3,5-trimethyl benzene). C9HiiN02,mw 165.21, N 8.48%, OB to CO2 —208.22%, rhmb cryst (from ale) ... 

Azido-4-nitro-mesitylene (2-Azido-4-nitro-1,3,5-trimethyl benzene). C9Hjo02N4 mw 206.23, N 27.17%, OB to COj -155.17%,... 

Needles+HjO (from aq eth), anhydr crysts (from abs eth), mp 23°. Can be prepd by adding Na azide to a soln of 4-nitro-mesitylene-diazonium chloride-(2) (Ref 2). Expls on fast heating in all org solvs. Loses 2/3 of its N content in conc sulfuric acid... 

Davies,jes 123,235(1923) CA 17,1633(1923) 2-NitraminO 4-ozido-6-nitro-mesitylene or N i tr amino me sitylene azo imide,... 

C,H,Cl2N0 gj 6-Nitro-mesitylen-disiiIfon-a tire-(2.4)-diohloild 11 U119. 

An alternative to the above mechanism is that acetoxylation is an addition-elimination process involving N02 and OAc , leading to nitro and acetoxy products77, and it follows that this process would be less likely to occur, for example, with mesitylene and significantly perhaps, experiments seeking acetoxylation in mesitylene have failed78 on the other hand, mesitylene is a very reactive substrate so it could be that an alternative nitrating species is involved here. 

Die Umwandlung von aliphatischen Nitro-Verbindungen mit Phenylisocyanat/Triethyl-amin, Phosphorylchlorid/Triethylamin, Essigsaurechlorid/Natriummethanolat oder 4-Methyl-benzolsulfonsaure/Mesitylen fuhrt iiber die Nitriloxid-Zwischenstufe und deren 1,3-dipolare Cycloaddition an Alkene bzw. Alkine zu den entsprechenden 4,5-Dihydro-l,2-oxazolens a-1 (s. Bd. E5, 1594-1595 X/l, 447-449). 

Auch die Reaktion von Azido-benzol und seinen Methyl-, Chlor- und Nitro-Derivaten mit Methyl-benzolen in Gegenwart von Bortrifluorid fuhrt in den meisten Fallen zu Gemischen von aromatischen Aminen, wobei man z.B. aus 4-Azido-l-methyl-benzol und 1,3-Dimethyl-benzol als Hauptprodukt (2,4-Dimethyl-phenyl)-(4-methyl-phenyl)-amin (67%) neben 4-Methyi-N-(3-methyl-benzyl)-anilin (7,5%) und 4-Methyl-anilin (5%) erhalt, aus l-Azido-4-methyl-benzol und Mesitylen jedoch (4- (Methyl-phenyl)-(2,4,6-trime-thyl-phenyl)-amin (55%) neben nur wenig 2,4,6-Trimethyl-anilin (1%)2. 

Distler, Blecher Lopex Explosives were patented safety expls consisting of nitro-xylenes as chief constituents. The nitro compds had varying amts of cumol, mesitylene xylene nitro constituents mixed with AN, other nitrates or KClOg or metal oxides. For example, if 12 parts nitrated solvent naphtha are intimately mixed with 88 parts of AN, a very insensitive expl is produced, which is unaffected by either shock or percussion which does not explode at 200° or in an open flame, but which has an extremely powerful shattering effect when suitably detonated Ref Colver (1918), p259... 

Some other aromatics azidated in this way included 1,2,3-trimethoxybenzene (at C-5), naphthalene (at C-l), mesitylene, etc. Mechanistic studies have shown that azide reacts as a nucleophile with aryl cation radicals formed through electron abstraction by BTI. With p-alkylanisoles bearing at least one benzylic proton, BTI and Me3SiN3 in acetonitrile gave sp3-C-substitution products, homolytically. Among the R groups were not only alkyls but also cyano, nitro and others [102]. 

The presence of nitro groups in diazonium compounds considerably facilitates coupling to yield azo-compounds. For example the diazonium salt of picramide couples readily with mesitylene [157],... 

Thus, nitro compounds with a great number substituents, for example trinitro-mesitylene, do not give any colour reactions. Compounds with nitro groups located in the 2,4-positions, produce colours that depend to a considerable extent on the substituent in position 1. The presence of the OH or NH2 group interferes with the colour reaction. The situation remains unchanged after both of the groups have been acylated, while alkylation of a phenol restores the ability to produce colour,... 

A further study of 2-nitraminopyridine and its 3-, 4-, 5-, and 6-methyl-, 5-bromo-, and 5-nitro derivatives showed that in sulfuric acid, free nitro-nium ions are produced (added mesitylene becomes nitrated). The relative rates of nitration at the 3- and 5-positions of the methyl derivatives are shown in Table 9.4. The results for the 4-methyl compound show that a normal SEAr mechanism is not involved. 5-Methyl-2-nitraminopyridine seemed to react by a different route since a considerable amount of 5-... 

Nitrile oxides This acid is an effective catalyst for dehydration of primary nitro compounds (RCH,NO,) to nitrile oxides, which can be trapped with dipolarophiles to form five-membered heterocycles. The reaction is carried out in refluxing mesitylene. 

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