Methyl nitroamine

Methyl((methylnitroamino)- methyl)nitroamine CH3N(N02)CH2N(CH3)-N02 40.0 167.4 Derived 2000KOS/MIR... 

In nitroamine oxides the nitro group may be reduced preferentially but usually both functions are affected. 5-Ethyl-2-methyl-4-nitropyridine A -oxide is converted quantitatively to 4-amino-5-ethyl-2-methylpyridine by hydrogen over 30% palladium on charcoal in ethanolic solution [737]. The outcome of the hydrogenation of a nitroamine oxide may be influenced by reaction conditions [736]. 

Nitration of the aminopyridines and their methyl derivatives reveals some interesting facets. The amino group strongly activates the positions ortho and para to itself towards nitration, but reaction proceeds via the N-nitroamines. 4-Aminopyridine undergoes nitration via the iV-nitroamine (65) to yield 4-amino-3-nitropyridine (equation 40). Nitration... 

The nitroamines are substituted ammonias, substances in which a nitro group is attached directly to a trivalent nitrogen atom. They are prepared in general either by the nitration of a nitrogen base or of one of its salts, or they are prepared by the splitting off of water from the nitrate of the base by the action of concentrated sulfuric acid upon it. At present two nitroamines are of particular interest to the explosives worker, namely, nitro-guanidine and cyclotrimethylenetrinitramine (cyclonite). Both are produced from synthetic materials which have become available in large commercial quantities only since the first World War, the first from cyanamide, the second from formaldehyde from the oxidation of synthetic methyl alcohol. 

When the author reacted 2-chloro-5-chloromethyl-thiazole, (II), with 3-methyl-4-nitroamine-l,2,3,6-tetrahydro-5-(2-chloro-thiazole-4-yl)-methyl-l,3,5-oxadiazine, the Step 3 product, 3-methyl-4-nitroamine-l,2,3,6-tetrahydro-5-(2-chloro-thiazole-4-yl)-methyl-l,3,5-oxadiazine, (III), was isolated. 

Bei der Synthese von 4-Amino-2-methylthio-l,3-thiazolen aus 4-Nitro-l-(methylthio-thiocarbonyl)-guanidin und Halogen-methyl-Verbindungen wird formal Nitroamin abgespal-ten. Mit 1,3-Dichlor-aceton kann die Reaktion zweimal ablaufen, so daB Bis-[l,3-thiazol-5-yl]-ketone entstehen ... 

Isothiazolo[5,4-c]-2,l,3-benzothiadiazole (502) has been prepared by two methods. In the first, 5-nitro-2,l-benzoisothiazole (498) was converted to the nitroamine (499) by treatment with hydroxyl-amine in basic solution this was reduced with iron and acetic acid, and the o-diamino product (500) cyclized to (502) with thionyl chloride. In a second approach, treatment of 5-amino-4-methyl-2,l,3-benzothiadiazole (501) with iV-sulfinylmethanosulfonamide also led to (502). The isothiazolo[4,5-c]-2,l,3-benzothiadiazole (504) has been synthesized from 4-amino-5-methyl-2,l,3-benzothiadiazole (503) by an analogous procedure (Scheme 39) <80JHC537>. 

Nitration of 2-amino-3-methyl-IbP proceeds at room temperature, but it is limited to the formation of a nitroamine. The attempt to rearrange this compound into a C-nitro derivative by heating with concentrated H2SO4 failed, as with 2- and 4-nitroaminopyridines. 

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