Mononitro derivatives

When nitration of pyridazine iV-oxides is carried out with acyl nitrates (prepared in situ from acyl chlorides and silver nitrate) the reaction takes place at the /3-position relative to the iV-oxide group. Under these circumstances only mononitro derivatives are formed. For example, nitration of pyridazine 1-oxide with acetyl nitrate yields 3-nitropyridazine 1-oxide (17%) and 5-nitropyridazine 1-oxide (0.8%), whereas with benzoyl nitrate a better yield of 5-nitropyridazine 1-oxide is obtained. 

Relatively little is known concerning the substitution reactions of the carbolines. The most studied reaction is that of nitration. Nitration of l-methyl-j8-carboline gave two mononitro derivatives. The highermelting isomer, which was formed predominantly (57% yield), was shown to be 6-nitro-l-methyl-j8-carboline (253 R = CH3) by its conversion into 6-bromo-l-methyl-j5-carboline the latter was synthesized unambiguously from 5-bromotryptophan and acetaldehyde. The lower melting isomer, recovered in 20% yield, was presumed to be the 8-nitro derivative (254), although this was not established. Nitration of j8-carboline with concentrated nitric acid at 35° has been reported to yield 6-nitro-j3-carboline (253 R = H) as the sole product. Only the 6-nitro derivatives (255) were isolated on nitration... 

Nitration of 5-niethoxyquinoxaline furnishes a dinitro derivative, presumably 5-methoxy-6,8-dinitrociuinoxaline, but no mononitro derivative could be isolated. ... 

With ten 7i-electrons delocalized over seven atoms, trithiadiazepine is electron rich and should undergo electrophilic substitution, which indeed it does. Nitronium tetrafluoroborate at — 10 C or copper(II) nitrate gives the mononitro derivative 5, which can be converted into the dinitro compound 6 by the action of an excess of nitronium tetrafluoroborate at 10 C.388... 

The nitration of N,N -diethylurea gives nitrated products which are precursors for a new energetic plasticizer N,N -dialkyl-N,N -dinitrourea (DNDA). For macroscopic batch processing, this reaction is characterized by a lack of selectivity owing to mononitro derivative formation and thermal decomposition of the dinitro product due to increasing temperature during the course of reaction [37, 38]. 

The isomeric dinitro derivatives, and some of the mononitro derivatives, are... 

Nitration of the ester with 90% nitric acid was effected according to a literature method. Examination of the reaction mixture by TLC showed that both expected mononitro derivatives had been formed, and it was allowed to stand at ambient temperature overnight. Ice and dichloromethane were then added, and the separated solvent layer was washed with aqueous sodium hydrogen carbonate, dried, and then freed of solvent by evaporation. The viscous oily residue decomposed and ignited in the flask. The preparation was repeated, but worked up immediately and under nitrogen while still cold, and furnished samples of both of the pine isomeric nitro derivatives. Thermal analysis of these showed both to be thermally stable. It was concluded that the decomposition was due to an impurity formed during the 16 h interval between nitration and work-up. 

The complete reduction of nitro-compounds which contain several nitro-groups is carried out in the same way as in the case of mononitro-derivatives. If, however, only partial reduction is desired, the use of ammonium hydrosulphide is advantageous. 

Tanaka et al. (1996,2000) studied the behavior of a series of naphthalene derivatives in AN solution containing NaN02 and CF3SO3H at 0°C in air. Naphthalene showed very low reactivity, and most of the starting material was recovered after the reaction. In case of 1-methylnaphthalene, a coupling reaction took place to produce 4,4 -dimethyl-l,T-binaphthyl in 91% yield alongside mononitro derivatives of the dimer in 1.5% yield. However, when the reaction is carried out on the same conditions but in inert (Nj) atmosphere, the yield of the dimer decreased from 97 to 15%, and no mononitro derivatives were formed. Therefore, the oxidation of NO with O2 to form NO2 (after the electron transfer to NO from 1-methylnaphthalene) is an obvious step of the reaction depicted in Scheme 4.42. 

Unlike Scheme 15, which shows the synthesis of symmetrical products 45 and 46, Scheme 16 illustrates the approach to the synthesis of unsym-metrical photochromes 49 and 50 starting from mononitro derivative 47, prepared in 75% yield from 44 (in a mixture with dinitro derivative 48). 

The mononitro derivatives of the 2-hydroxy 8-hydroxy quinolines are stable (Beil 21, 99-100). The di tri-nitro derivatives are less stable but not really explosive. These are described below... 

Iodotoluene, CH3C6H4I, is a stable non-explosive compd so are its mononitro derivatives. Higher nitro derivs or azido derivs were not found in Beil Ref Beil 5, 310 337... 

The introduction of a nitro group at the orl/jo-position to the oxygen atom in 4-diazo-1-oxide (IV) increases the stability. Great stability is also demonstrated by the 0- and p-substituted nitro derivatives of 2-diazo-l-oxide (VI and VII). On the other hand, the m-substituted compound (VIII) has a lower stability than compounds (VI) and (VII). Dinitro substituted derivatives, ortho-ortho (V) and orthopara (Ila), are distinguished by a higher stability than the mononitro derivatives of the same oxides (IV) or (VI) and (VII). 

Other props methods of prepn of the mononitro derivs are given in the Refs Refs 1) Beil 13, (39) [60 ] 2) Beil 13,... 

Its mononitro deriv, Bis(a, a-dimethyl-p-nitrobenzyl Peroxide, jp-03N.C6H4C(N03)20-]2> crysts(from ale), mp 158°(decompn), was prepd by Hock 8c Kropf (Ref 4)... 

Dinitro-l,2-diethylbenzene, yel prisms (from ale), mp 89-90° was obtd, in addn to mononitro derivs, on nitrating 1,2-diethylbenzene (Ref 2). No expl props were reported... 

Other mononitro derivatives are not of such importance. They are ... 

Baker controlled the kinetics of the reactions (52) and (53) in the presence of ethyl alcohol, phenol and its mononitro derivative. 

Nitration of arenes. Reaction of 1-naphthol with CAN in acetic acid results in 2,4- and 4,6-dinitro derivatives. The reaction with CAN absorbed on silica gel results in 2-nitro- and 4-nitro-l-naphthol in 42 and 38% yield, respectively. Polynuclear arenes are not oxidized to quinones by CAN supported on silica but are converted mainly into mononitro derivatives. Thus phenanthrene is converted into 2-nitrophenanthrene (45% yield) and 3-nitrophenanthrene (28% yield).1... 

All mononitro derivs form salts and addn compds, such as hydrochloride, nitrate, picrate, etc. Their other props and methods of prepn are given in the Refs... 

The expl props of the mononitro derivs were not detd... 

Berl found that the speed of decompn of nitro-compds increased with an increase in the number of nitro groups present. Mononitro derivs showed results which were too low (Ref Private communication from Dr E.Berl to Dr B-T-Fedoroff about 1943). This method can be used also when it is desired to determine the N content of nitrocompds... 

See also Mononitro deriv of Desoxyinositol Refs l)Beil 31, 63 2)J.M.Grosheintz H.O. 

The treatment of 4-methyl-l,8-naphthyridine-2,7-dione with fuming nitric and sulfuric acids is reported to give a mononitro derivative of uncertain structure.146... 

Dimethoxy- and 5,6-methylenedioxybenzo[6]thiophene undergo bromination, Vilsmeier-Haack formylation, and Friedel-Crafts acetylation in the 2-position (see Section VI, A).189 With nitric acid, however, 5,6-methylenedioxybenzo[6]thiophene affords an unidentified mononitro derivative, which is not the 2-nitro compound.548... 

Thioindoxyl-1,1-dioxide is monobrominated271, 751 and mononitrated 751,755 in the 2-position. The mononitro derivative reacts with bromine, chlorine, or iodine to give the corresponding 2-halo-2-nitro-... 

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