1.1.1- Trinitromethane, reactions

One attempted reaction of trinitromethane with impure ketone caused an explosion at refrigerator temperature. 

In reactions of certain alkyl halides with salts of polynitromethanes, C-alkyla-tion can also be diminished and target O-nitronates can be prepared in satisfactory yields (21, 22) (Scheme 3.8, Eq. 2). Of special note is the study by Kim and Adolph (22), who prepared numerous nitronates by alkylation of salts of dinitromethane, cyanodinitromethane, and trinitromethane with a representative series of a-chloro-substituted (including functionalized) ethers. 

In this manner, the Ag salt of trinitromethane is involved in cascade reactions with branched alkyl halides to give unexpected products. 

It has been expected that trinitromethane derivatives of the general formula (NC>2)3C — M (M is K, Cs, SiMe3, or SnBuj) can generate dinitrocarbene through solvolysis, and the latter can react as a 1,3-dipole with some olefins (74). However, a next study (75) demonstrated that this interpretation of the processes is erroneous at least for M=SiMe3. Attempts to detect nitrocarbenes in cycloaddition reactions during thermolysis or photolysis of aliphatic nitrodiazo compounds also failed (76). 

In addition to conventional generation of carbenes from nitrodiazo compounds (22) (79), target intermediates C can be prepared by oxidation of functionalized AN CH2XNO2 with phenyliodonium diacetate. The reactions of Rhodium intermediates with certain olefins afford the corresponding cyclopropanes (23). The cycloaddition reaction was performed in the presence of a catalyst. (The successful synthesis of nitrocyclopropanes from trinitromethane derivatives and nitroacetic ester was also documented (81)). 

Approximately at the same time, Shevelev and coworkers studied the reactions of trinitromethane and 1,1-dinitroethane salts with RCOC1 (R=Me or Ph) and detected the corresponding acyl nitronates on the basis of decomposition products and by trapping with various E—X reagents (222) (Scheme 3.64). 

The chemistry of O-acyl derivatives of trinitromethane was studied in more detail. By analogy with O-silyl ethers of trinitromethane, for intermediate (120) (Scheme 3.103, Eq. 1) it was suggested (222a) that the reaction involves elimination of acetyl nitrate to form the very unstable N-oxide A, which adds acetyl chloride to give derivative (121). Saponification of the latter affords isolable oxime (122). 

The reaction of alkynes with nitric acid or mixed acid is generally not synthetically useful. An exception is the reaction of acetylene with mixed acid or fuming nitric acid which leads to the formation of tetranitromethane. A modification to this reaction uses a mixture of anhydrous nitric acid and mercuric nitrate to form trinitromethane (nitroform) from acetylene. Nitroform is produced industrially via this method in a continuous process in 74 % yield. " The reaction of ethylene with 95-100 % nitric acid is also reported to yield nitroform (and 2-nitroethanol). The nitration of ketene with fuming nitric acid is reported to yield tetranitromethane. Tetranitromethane is conveniently synthesized in the laboratory by leaving a mixture of fuming nitric acid and acetic anhydride to stand at room temperature for several days. ... 

The intermolecular alkylation of metallo nitronates with various alkyl halides is limited. The addition of methyl iodide to the silver salt of an aryl nitro-methane provides the corresponding methyl nitronate in moderate yield (Eq. 2.13) (150), which has also been extended to the silver salt of trinitromethane (Scheme 2.16) (151-153). However, in the case of primary halides, both O- and C-alkylation are observed. For secondary and tertiary halides, only O-alkylation is observed, but in low yields. Unfortunately, under the reaction conditions, the starting alkyl halide can undergo dehydrohalogenation to provide the corresponding alkene, which then undergoes [3+2] cycloaddition with the alkyl nitronate. 

Isoxazoleazo Derivatives of Trinitromethane Prepared from Acetylene. In studying the reaction products of nitric acid with acetylene, Quilico isolated an explosive product of yellow color corresponding to the formula C4H207N6, mw 246.10, N 34.15%... 

Delft University of Technology and the University of Delaware) is hydrazinium nitroformate [N2H5.C (N02)3 Structure (4.2)] a salt of hydrazine (N2H4) and nitro-form or trinitromethane [HC(N02)3], reported to have been discovered in 1951. Of course, this is made without the use of N205. It is prepared as a precipitate [74] by acid-base reaction between nitroform and hydrazine, Equation 4.18. 

CH3. C.NH.CH2. C(.N02)3, C4H6N406 mw 206.14 N 27.19% OB to C02 -38.81% white ndles mp 91—92°. Sol in hot ethanol-w mixt. Prepn is as follows Acetamide in satd aq Ba hydroxide is mixed with 37% formalin at RT, then satd with C02 and filtered. The filtrate is then mixed with 4.5p of trinitromethane, the soln left standing a few minutes, and then heated at 75—80° to complete the reaction. After re-crystn of the crude product from ethanol-w a 46% yield is obtd. The compd has an impact sensy of 35cm using a 2.5-kg wt Refs 1) Beil, not found 2) P.O. Tawney,... 

The exocyclic amino group of 5-aminotetrazole is reactive in nucleophilic substitution of halogen atoms in halonitrobenzenes. For example, the synthesis of 5-picrylaminotetrazole 406 is based on this process <1999THS(3)467>. Finally, 5-aminotetrazole and l-methyl-5-aminotetrazole 407 undergo a Mannich reaction with formaldehyde and trinitromethane with formation of products 408 (R = H, Me) . 

Although tetranitromethane does not contain active hydrogen it readily enters certain reactions. With water it reacts slowly to form trinitromethane, i.e. nitro-... 

The starting material 2,2,2-trinitroethanol (1) was prepared from the reaction of trinitromethane with formaldehyde (see Fig. 9.18). 

The synthesis of hydrazinium nitroformate (HNF) occurs best through the reaction of anhydrous hydrazine with trinitromethane (nitroform) in methanol or diethyl ether ... 

Penczek et al. polymerized oxetane in nitrobenzene with trinitromethane. They proved the termination to be a bimolecular reaction... 

Flammable liquid. A very dangerous fire hazard when exposed to heat, flame, or oxidizers. Moderately explosive when exposed to heat or flame. Reacts with air to form dangerous peroxides. The presence of 2-butanone increases the reaction rate for peroxide formation. Hydrogen peroxide sharply reduces the autoignition temperature. Violent explosive reaction when heated with aluminum isopropoxide + crotonaldehyde + heat. Forms explosive mixtures with trinitromethane, hydrogen... 

Higher nitrated derivatives of phenylnitromethane, among them those of derivatives of dinitro- and trinitromethane (VoL 1, p. 399) are important. The reaction of Ponzio [82] consists of acting with N2O4 on benzaidoxime phenyl-dinit rome thane results (16) ... 

Hanizsch and Kinkenberger (171] established that TNM can quantitativel> be hydrolysed to trinitromethane by potassium hydroxide or potassium eih oxide. However, aqueous concentrated KOli can produce a deeper hydrolysis with the formation of KNO3, KNOi and K2CO3 (172]. The reaction of tlu formation of trinitromethane ( nitroform ) from TNM became a standar. method of making nitrotonn used for thesis of polynit ro aliphatic com pounds. 

Several 2-substituted pyridines 73 can be prepared by reactions of N-fluoropyridinium triflate (72) with triethylamine in various solvents. A novel carbene has been proposed as the reactive species (87TL2705). Treatment of N-fluoropyridinium fluorides 74 with trinitromethane gives trinitromethyl-... 

Tetrazoles. - The high-pressure reaction of phenyl azide with dicyanogen yields 5-cyano-l-phenyltetrazole (510). The (trinitromethyl)tetrazole (511) has been prepared by the action of trimethylsilyl azide on cyano-trinitromethane. 5-Aryltetrazoles (512) are transformed into the oxadia-zoles (513) by reaction with aroyl isothiocyanates Ar CONCS. The... 

Thus, for trinitromethane, the explosive decomposition reaction would be... 

A well stirred solution of 17.9 g 2,3,4,5-tetramethoxypropenylbenzene in 80 mL distilled acetone was treated with 6.9 g pyridine, and cooled to 0 °C with an external ice bath. There was then added 14 g tetranitromethane over the course of a 0.5 min, and the reaction was quenched by the addition of a solution of 4.6 g KOH in 80 mL H20. As the reaction mixture stood, there was a slow deposition of yellow crystals, but beware, this is not the product. This solid weighed 4.0 g and was the potassium salt of trinitromethane. This isolate was dried and sealed in a small vial. After a few days standing, it detonated spontaneously. The filtrate was extracted with 3x75 mL CH2CI2, and the removal of the solvent from these extracts gave a residue of 20.8 g of crude 2-nitro-1-(2,3,4,5-tetramethoxyphenyl)propene which did not crystallize. 

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