N-nitro derivatives

Nitro-bakterien, n.pl. nitrobacteria, -benzol, -benzin, n. nitrobenzene, -chinon, n. nitro-quinone. -cocussaure, /. nitrocoeeic acid, -derivat, n. nitro derivative, -farbstoff, m. nitro dye. -fettkorper, m. aliphatic nitro compound, -fettsaure, /. nitro fatty acid, -gruppe, /. nitro group, -halogenbenzole,... 

If a functional group in N-nitro derivatives attaches to the nitrogen atom, a two processes which are presented in Scheme 3.77 and proceed at different rates, can be observed by dynamic NMR (290). 

Semenczuk and T. Urbanski also showed that dimethylaniline may be nitrated to tetryl by a mixture of nitric acid with acetic acid or acetic anhydride. As yet the only other results mentioned in the literature with reference to this method are those of Orton [11]. He asserted that dimethylaniline gives no N-nitro derivative when reacted with a mixture of nitric acid with acetic anhydride or acetic acid he obtained only 2,4-dinitromethylaniline. 

Primary Amide N-nitro derivative, % °C. Calculated C H N C Found H N... 

Aliphatic and alicyclic carbamates are nitrated smoothly and in excellent yields by a nitric acid-acetic anhydride mixture (4). Similarity, we have found that treating an acyl aliphatic amine and a urethane with one equivalent of nitronium tetrafluoroborate in acetonitrile at —30° C. gave the corresponding N-nitro derivatives in good to excellent yields. However, diacylamines are more difficult to nitrate, and Kauffman and Burger (9) have reported that nitrating succinimide required 13 hours... 

Cyclic N-nitro-derivatives starting from hexamethylenetetraamine are similarly obtained. Acyclic Mannich ba.ses of methylmercaptan have also been subjected to nitration. - ... 

Nitration of triazole and its C-monoalkyl derivatives fails. Aryltriazoles are nitrated on the benzene ring but 3-p-nitrophenyltriazole (112) in which the benzene ring is deactivated affords the N-nitro derivative (113). This rearranges to the C-nitro compound (Scheme 36) through an isotriazole intermediate on kinetic evidence for a first order intramolecular rearrangement (72CC37). 

S830). Use of the N-nitro derivative 152 (R = NOz) gave the N-nitro-diazocines 153 (R = N02 R1 = H, Me) (83S830). There have been two reports of reaction of Af-methyl-p-toluidine with acidic formaldehyde solution to yield the diazocine 67 (R -R3 = H, R4 = R5 = Me) (76CI(L)1644). Similarly, reaction of formaldehyde with diphenylamine afforded... 

Compound Yield of N-Nitro Derivative, % Compound Yield of N-Nitro Compound, %... 

Amides(acylamines) and urethanes as shown by Olsen [107] gave with one equivalent of NO2 BF in acetonitrile at -30 C the corresponding N-nitro derivatives (Table XXVI). 

The reaction of NO2 BF4 with A-alkylamides has been investigated [107,111] under different conditions, but nevertheless the results permit the conclusion that at a low temperature (-30 C), N-butylacetamide and ethyl n-butylcarbamate in acetonitrile are nitrated to the N-nitro derivatives [107] while at higher temperatures, (up to +10 C) nitrolysis takes place with formation of the corresponding carboxylic acid and alcohol as well as N2O [121]. The question as to which C—N bond is N-nitrated and cleaved in the reactions of A-alkyJamides with NO BFJ requires additional study. 

It is not clear whether the N-nitrocyanamides are formed via isomerization of the N-nitro derivative or not. 

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