Methylnitramine

Trimethyl benzene 2.4.6- Trinitrophenol, see Picric acid 2.4.6- Trinitrophenyl-methylnitramine, see Tetryl CT... 

Me NENA. Designation for N-(2-mtroxypropyl) methylnitramine, described under N-methyl-n-(2-nitroxypropyl) nitramine in this Vol... 

Methylnitramine/reacts with diazonium salts to form ArN NNMeN02 which are yellow solids that ignite below their mp and decomp on standing at room temp (Ref 1). It reacts with activated olefins to form adducts of the type XCH2CH2NMeN02 where X is an activating group (Ref 2)... 

Registry No 19092-03-6. It has been shown to be an intermediate in the prepn of Tetryl from N,N-dimethylaniline as it can be prepd from N,N-dimethylariiline or 2,4-dinitro-N-methylaniline by the action of 70% nitric acid in 90% yield (Refs 13 14) and can be nitrated to Tetryl with a mixt of 64% sulfuric acid, 15% nitric. acid, and-21%-w yield 91.9% (Ref 14). It can be isolated from commercial Tetryl and identified by thin layer chromatography (Ref 21) N,2,6-Trinitro-N-methylaniline (2,6-dinitrophenyl-methylnitramine), mp 110.8 874.9kcal/... 

N, 2,3,4-Tetranitro-N-methylaniline (2,3,4-trinitrophenyl-N-methylnitramine), mp 122.5° prepd by the nitration of 2,3,5-trinitro-N-niethyl-aniline with nitric acid (concn unspecified)... 

N 36.83%, OB to C02 -42.1% colorless needles from ether nip 38° d 1.243 at 49/4° RI 1.4616 at 48,6°. V sol in cold w, ale, chlf and benz less sol in eth and still less sol in petr eth. Can be prepd by nitrating n-methyl-urethane with abs nitric acid. The resulting soln of methyl nitrourethane is drowned in w, neutralized with Na carbonate, and extrd with eth to remove methyl nitrourethane. On passing ammonia gas thru the eth extract, a white ppt of the ammonium salt of methylnitramine is deposited and sepd by filtration. It is disd in ale and boiled to drive off the ammonia, and... 

Methylnitramine explodes on heating or on contact with coned sulfuric acid. Based on tests conducted in the USA during WWII, it is more powerful than TNT (144% as detd by Trauzl lead block test) (Ref 3) ... 

Potassium Methylnitraminate. K.CH302N2 fine needles, which expl violently on heating. 1 According to Davis (Ref 2), the heavy metal salts of methylnitramine are primary explosives, but have not been investigated extensively Refs 1) Beil 4, 567, (568) [968]... 

Synonyms BRN 0964788 CCRIS 3143 CE EINECS 207-531-9 7V-Methyl-2,4,6-tetranitro-aniline -Methyl-iV,2,4,6-tetranitrobenzenaniine Nitramine NSC 2166 Picrylmethyl-nitramine Picrylnitromethylamine Tetralit Tetralite Tetril 2,4,6-Tetryl Trinitrophenylmethyl-nitramine Trinitrophenyl-7V-methylnitramine 2,4,6-Trinitrophenylmethylnitramine 2,4,6-Trinitro-phenyl-A7methylnitramine UN 0208. 

Trinitrophenol, see Picric acid Trinitrophenylmethylnitramine, see Tetryl Trinitrophenyl-fV-methylnitramine, see Tetryl... 

Trinitrophenyl-fV-methylnitramine, see Tetryl Trinitrotoluene, see 2,4,6-Trinitrotoluene s/m-Trinitrotoluene, see 2,4,6-Trinitrotoluene Trinitrotoluol, see 2,4,6-Trinitrotoluene a-Trinitrotoluol, see 2,4,6-Trinitrotoluene... 

Other reagents have been used for the direct nitration of amines under nonacidic conditions. Mandel reported the synthesis of methylnitramine, dimethylnitramine and diisopropy-Initramine from the reaction of nitryl fluoride with the parent amine. The presence of an excess of amine appears to be of prime importance given that other reports give the nitrosamine as a major by-product. 

Methylnitramine (1) can be prepared from the hydrolysis of an appropriate secondary nitramide. One route involves the nitration of Ai, Ai -dimethylsulfamide (54) to Ai,Ai -dinitro-iV,iV -dimethylsulfamide (10) with absolute nitric acid, followed by ammonolysis and subse-... 

Methylnitramine (1) has also been synthesized from the hydrolysis of ethyl Ai-methyl-A -nitrocarbamate (163), Al,Al -dinitro-Ai,Ai -dimethyloxamide (9) and A Ai -dinitro-Ai.Al -dimethylurea (165) " the latter, synthesized from the mixed acid nitration of N,N -dimethylurea (164), has been suggested as a possible industrial route to methylnitramineX" ... 

Davis studied the dehydration of urea nitrates as a route to iV-nitroureas. The nitrate salt of iV-methylurea undergoes dehydration-rearrangement on treatment with concentrated sulfuric acid to give Af-nitro-A -methylurea in 42 % yield. In this compound the nitro and methyl groups are attached to the same nitrogen and so its hydrolysis can provide a route to methylnitramine. In contrast, the nitrate salts of ethyl, n-propyl, n-butyl and n-amyl ureas, give iV-nitro-A -ethylurea (49 %), A -nitro-A -propylurea (60 %), iV-nitro-iV -butylurea (67 %) and iV-nitro-A -amylurea (67 %), respectively, on treatment with concentrated sulfuric acid. 

Agency for Toxic Substances and Disease Registry (ATSDR) Toxicological Profile for Tetryl (2,4,6 Trinitrophenyl-N-Methylnitramine) pp 1-100. US Department of Health and Human Services, Public Health Service, 1995... 

Hydroxy- and Amino-methylnitramines. A review with 93 refs of the chemistry of nitramines is reported by Lamberton (Ref)... 

N-(fi-Hydroxyethylj-methylamine. Its nitrated deriv N-(j3-Nitroxyethyl)-methylnitramine (MeNE-NA). 02N0.CH2.CH2.N(N02).CH3 mw 165.11,... 

Meiayaku (Army), Sanshoki (Navy ) or Mechiru Nitroamin. Tetryl or 2,4,6-Trinitrophenyl-methylnitramine,... 

Trinitro - 3 - methylphen ol N-Methyl gluconamide pentanitrate Methylnitramine... 

Formaldehyde, Methylnitramine, Methylene chloride, Magenesium sulfate. Sulfuric acid. Chloroform, Hexane Nitric acid. Diethanolamine, Ethanol, Ether, Acetone Potassium permanganate, 3-Amino-l,2,4-triazole, Sodium hydroxide. Sodium bisulfite. Hydrochloric acid. Nitric acid, Acetic anhydride. Acetone... 

Formaldehyde, Methylnitramine, Methylene chloride. Magnesium sulfate. Sulfuric acid. Chloroform, Hexane... 

Because of their favorable elemental compositions, heteroaromatic nitro compounds represent explosives of high performance (oxygen balance, density, heat of formation and VOD) compared with analogous aromatic explosives [136-138]. With this objective, Licht and co-workers have synthesized some methylnitramine substituted pyridines and triazines, established their structures and characterized them for thermal and impact sensitivities [139]. The data on impact sensitivity, however, indicate that tetryl may not be replaced by these explosives. 

This view was generally accepted. It was based, however, not so much on experimental evidence as on Hantzsch s personal authority. In point of fact Euler [12] found that the rate of formation of the ammonium salt is by no means as slow as Hantzsch believed and expressed doubt as to the existence of the supposed tauto-merism. No further evidence confirming the existence of the aci-form was forthcoming until the O-alkyl derivatives, e.g. O-methyl-methylnitramine (III),... 

Concentrated nitric acid decomposes some primary nitramines methylnitramine, for example, is decomposed by anhydrous nitric acid, even at a temperature below 0°C, to form methyl nitrate and N20 (Franchimont [16]). 

Thus, methylnitramine is converted into dimethylnitramine and phenylnitramine nto phenyl-O-methylnitramine ... 

This is a powerful explosive, stronger than tetryl but weaker than cyclonite. It is, however, of no practical value chiefly because its preparation is too expensive, requiring first the conversion of methylamine into urethane and then into its nitro derivative. On hydrolysis the latter yields methylnitramine. Similarly, the hydrolysis of dinitrodimethyloxamide (p. 35) leads to the formation of methylnitramine. 

Methylnitramine is very readily soluble in water, alcohol, chloroform and benzene but is less soluble in ether. It is a strong acid which easily forms salts, including explosive ones. It is not decomposed by boiling water, even in the presence of alkalis, but it is liable to destructive distillation yielding dimethylnitramine (CH3)2NN02, m.p. 57°C, methyl alcohol, nitrous oxide and many other products. 

Methylnitramine decomposes explosively in contact with concentrated sulphuric acid. It is evolved when aniline reacts with tetryl, a diphenylamine derivative (p. 51) is produced simultaneously. Methylnitramine reacts with picryl chloride to form tetryl. The structure of tetryl (p. 40) was first proved by this synthesis. 

The product of nitration of dimethyloxamide is soluble in nitric acid and is separated by pouring the solution into water. It decomposes on treatment with concentrated sulphuric acid or on boiling with aqueous ammonia or barium hydroxide solution, forming the corresponding methylnitramine salt. Similarly, long-continued boiling in water results in complete decomposition, with the formation of oxalic acid and methylnitramine. 

The key representative of aromatic nitramines is the trinitro derivative of phenyl-methylnitramine—tetryl. This is 2,4,6-trinitrophenyhnethylnitramineorpicrylmethyl-nitramine or N-2,4,6-tetranitro-N-methylaniline. 

Tetryl combines with aniline in benzene solution even at room temperature to form 2,4,6-trinitrodiphenylamine (XII) and methylnitramine ... 

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