Trinitromethane Derivatives

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)). 

Scheme 3.103). In these experiments, a representative series of trinitromethane derivatives (NC C-E was isolated in various yields.

Nitroform. Same as Trinitromethane see under Methane and Derivatives in this Vol... 

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). 

Grakauskas, V. et al., J. Org. Chem., 1978, 43, 3485-3488 Trinitromethane ( nitroform ), dinitroacetonitrile, their salts and polynitroalkanes are all potentially dangerous, and must be carefully handled as explosive compounds [1], Many congeners and derivatives of dinitromethane are explosive and require careful and appropriate handling [2], Individually indexed compounds are ... 

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%... 

Phenyldiazonium mtroformate. Nitroform derivative (XIII) is of particular interest among derivative diazonium salts. It was prepared by Ponzio [21] who reacted the potassium salt of trinitromethane (nitroform) with an aqueous solution of phenyldiazonium acetate ... 

Complexes between tetranitromethane (which is a powerful electron acceptor) and different electron donors (aromatic substrates, alkenes, amines, sulphides, ethers) may be observed and isolated as moderately stable coloured complexes (if stored in the dark). These complexes are usually classified as CT complexes. Irradiation of complexes between alkenes and trinitromethane forms interesting products, which are derived from the nucleophilic attack of the trinitromethide. 

Ponzio [95] obtained unstable aromatic azo derivatives of trinitromethane (of the type III) by reacting the ammonium salt of trinitromethane with diazonium salts ... 

W. S. Reich [96] prepared aromatic derivatives of trinitromethane (of the type IV) by acting with the silver salt of nitroform on ar-alkyl chlorides, as for example p- nitrobenzyl chloride ... 

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) ... 

Khisamutdinov et al. showed that the difluoramino group in various (di-fluoramino)dinitromethane derivatives could be displaced by azide anion to make azidodinitromethyl derivatives [88,89]. In contrast, a nitro group in (di-fluoramino)trinitromethane was displaced by nucleophiles such as fluoride and nitrite [90,91]. The nitrite by-product keeps yields low by competitive reaction with the starting material, resulting in (difluoramino)dinitromethane anion side product. With bromide nucleophile, the course of reaction was unexpectedly complex, as the initial bromo(difluoramino)dinitromethane im-... 

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