2.4.6- trinitrophenyl compounds

Some energetic compounds have picryl groups (2,4,6-trinitrophenyl-) introduced as substituents in the 3- and 4-positions of the furazan ring. Coburn synthesized a series of picrylamino-substituted furazans, including 4,4 -bis(picrylamino)-3,3 -bifurazan (BPABF) (34) from the reaction of 4,4 -diamino-3,3 -bifurazan (DABF) (32) with two equivalents of picryl fluoride. 

Two derivatives of this system (130 R = Me, = SO2Me and 2,4,6-trinitrophenyl) have been obtained by base treatment of the corresponding iodides (131). The crystal structure of compound 130 (R = Me, R = SOjMe) has been determined. 1,3-Dipolar reactivity of these betaines (130) has not been observed. 

See 2,4,6-Trinitrophenyl-(l-methylol)propyl-nitramine Nitrate] 7)A.D.Little,Inc, Report on Study of Pure Explosive Compound, Cambridge,Mass,.v 4(1952) Compd No 305, p 586(Part of rept is unclassified)... 

Sitzman, Synthesis of 2,4,6-Trinitrophenyl Derivatives of Heterocyclic Compounds , JHeterocyclChem 1977, 14 (7), 1151—55 ... 

The basicity of simple 4,5-dihydropyrazoles (A -pyrazolines) has been discussed on the basis of protonation at N-1 in the case of 1-unsubstituted, 1-methyl, and 1-phenyl derivatives <2000JP0372>. The pA values of 15 4,5-dihydropyrazoles substituted at N-1 by /i-nitrophenyl, 2,4-dinitrophenyl, and 2,4,6-trinitrophenyl groups were determined. After examining some linear free energy relationships, to discuss these values further, DFT calculations, including temperature effects, were carried out on the parent compounds (no C-substituents) for the 1-unsubstituted, 1-methyl, 1-phenyl, l-/)-nitrophenyl, and 1-(2,4,6-trinitrophenyl) series. These calculations predicted an inversion of N-1 and N-2 basicities between 1-phenyl- and l-(/>-nitrophenyl)-4,5-dihydropyrazoles. Since there were no experimental data for the protonation of 4,5-dihydropyrazoles in the gas phase, chemical ionization mass spectrometry was used to try to determine the structure of protonated 1-methyl- and l,3-dimethyl-5-phenyl-4,5-dihydropyrazoles. The substituent effects and protonation sites of 1-phenyl-3-methyl-5-A-benzylideneaminopyrazoles were studied by NMR and ab initio (6-31G ) MO calculations <1996J(P2)2383>. 

Diphenylpicrylhydrazyl, which is prepared from MA -diphenyl-A -(2,4,6-trinitrophenyl)hydrazine by oxidation with lead dioxide [982], is used for the dehydrogenation of 1,4-dihydronaphthalene to naphthalene and of hydrazobenzene to azobenzene [983]. Simpler and cheaper compounds are, however, available for such purposes (equation 21). 

Trinitrophenyl-P-hydroxynitraminoethyl nitrate (peniryl. pentyl) Hexanitrodiphenyl-f3 hydruxynitrarrinocihyl nitrate Nitraminonitrophenols Nicramino-azoxy compounds Nitro methylene blue Literature... 

Dye intermediates were early on adapted to the production of explosives. While most modern explosives are aromatic nitro compounds, ancillary products incorporate amino groups. Of interest here are two tetranitroanilines. Tetryl (2,4,6-trinitrophenyl-A-methylnitramine, or A,2,4,6-tetranitro-iV-methylaniline) (40) is employed as a booster for TNT. It can be made from V-methylaniline (39), or the cheaper V,V-dimethylaniline (32), since the latter loses one methyl group on oxidation. An alternative route, introduced in World War II, starts with conversion of dinitrochlorobenzene into dinitro-lV-methylaniline, which is then nitrated. The explosive tetrotyl is 70% tetryl and 30% TNT. 

UV, IR, and H NMR spectroscopic studies of 2-(phenylamino)pyrimidine showed that this compound exists as a tautomeric mixture containing only a small amount (ca. 0.2%) of the imino tautomer in an aqueous ethanolic solution (Kt=5. 5 x 102, amino/imino tautomer), but the Ky value is considerably smaller than that of 2-(phenylamino)pyridine (80BCJ717). The amino tautomer was also found to be highly predominant in solutions of 2-(phenylamino)-4,6-dimethylpy-rimidine (84H(22)2591) and 2-[/V-(2,4,6-trinitrophenyl)amino]pyrimidine in both polar and apolar solvents (92JHC1461). For cyclohexane-fused 2-aminopyrimidines 54 (X = NH2 R = CF3) and 55 (X = NH2 R = CF3 Ar = 4-Et2NC6H4), both amino and imino tautomers are present in the solid state however, only amino tautomers were observed in CHC13 solution (00S1738). 

Good examples are the compounds obtained by reaction of alkoxide ions with alkyl 2,4,6-trinitrophenyl ethers ... 

Harada et al. [18] reported the synthesis of a [2]rotaxane capped by j6-CD and a trinitrophenyl group. The /i-CD at the end binds the trinitrophenyl group stopper of another [2]rotaxanes gives a rotaxane aggregate, as shown in Fig. 2. Liu et al. [19] also developed a simple strategy to prepare polyrotaxane-like supramolecules. An inclusion compound had been synthesized by the complexation of 4,4 -di-pyridine and j6-CD in water the subsequent coordination of the complex with nickel ions in aqueous solution gave the corresponding pseudopolyrotaxane. 

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