6478-31-5Relevant academic research and scientific papers
Transient Nitronic Acid Formation in the Acid-Catalyzed Decomposition of Nitrobenzofuroxan and Nitrobenzofurazan ?-Adducts in Methanolic Solution. A Kinetic Study
Terrier, Francois,Ah-Kow, Guy,Chatrousse, Alain-Pierre
, p. 4583 - 4589 (1985)
Kinetic data for the acid-ctalyzed and uncatalyzed decomposition of the dioxolane spiro complexes of 7-(2-hydroxyethoxy)-4-nitrobenzofurazan and -benzofuroxan and of the 7,7-dimethoxy complexes of 7-methoxy-4-nitrobenzofurazan and -benzofuroxan have been obtained over a large pH range in methanol.The ring opening of the spiro complexes but not the methoxide ion departure from the dimethoxy adducts is found to be appreciably catalyzed by carboxylic acids.The corresponding Broensted α coefficients are equal to about 0.5, indicating concerted acid catalysis.At low pH, i.e., pH a values associated with the ionization of the resulting nitronic acids are all very similar and of the order of 4.2 - 4.5, as compared with estimated pKa values of about 1 - 2 for analogous nitronic acids of picryl ?-complexes.Kinetic data for the formation of the adducts are also reported.The marked differences observed in the rates of formation and decomposition of the similarly stable benzofurazan and benzofuroxan spiro adducts are interpreted in terms of electrostatic effects connected with the presence of the N-oxide group in the transition states for the benzofuroxan reactions.
REACTIONS OF AROMATIC NITRO COMPOUNDS. LXIV. ANIONIC ? COMPLEXES OF THE ALKYL ETHERS OF 2,4,6-TRINITROPHENOL WITH THE ALCOHOLATES OF DIHYDRIC AND TRIHYDRIC ALCOHOLS
Mel'nikov, A. I.,Gitis, S. S.,Kaminskii, A. Ya.
, p. 268 - 274 (2007/10/02)
Sodium 1-methoxy-1-(β-hydroxypropoxy)-2,4,6-trinitro-2,5-cyclohexadienide was obtained from 2,4,6-trinitroanisole and sodium 2-hydroxypropoxide.It was then converted into corresponding spirocyclic anionic ? complex.In the reaction of 2,4,6-trinitrophenetole with sodium 2-hydroxyethoxide, 3-hydroxypropoxide, and 4-hydroxybutoxide the 1-ethoxy-1-hydroxyalkoxyl ? complexes are formed at the first stage and are then converted into spirocyclic and 1,1-dihydroxyalkoxyl ? complexes.Spirocyclization only takes place in the presence of the β-hydroxy group.The transformations are realized with the participation of the glycol ethers of 2,4,6-trinitrophenol, which are formed in the reaction as transetherification products.
REACTIONS OF AROMATIC NITRO COMPOUNDS. LX. MECHANISM OF TRANSFORMATIONS OF SODIUM 6,8,10-TRINITRO-1,4-DIOXASPIRODECA-6,9-DIENIDE IN AN ACIDIC MEDIUM
Shakhkel'dyan, I. V.,Glaz, A. I.,Gitis, S. S.
, p. 2176 - 2179 (2007/10/02)
The effect of 2,4,6-trinitrophenol on the decomposition rate of sodium 6,8,10-trinitro-1,4-dioxaspirodeca-6,9-dienide in aqueous and water-dimethyl sulfoxide media was investigated.It was shown that the 1-(β-hydroxyethoxy)-2,4,6-trinitrobenzene formed during the decomposition of sodium 6,8,10-trinitro-1,4-dioxaspirodeca-6,9-dienide isomerizes with the formation of a spirocyclic quinolnitronic acid.Proton transfer in the isomerization takes place by an intermolecular mechanism with the participation of water.
REACTIONS OF AROMATIC NITRO COMPOUNDS. LVII. REACTION OF GLYCOL ETHERS OF PICRIC ACID WITH NUCLEOPHILIC AGENTS
Mel'nikov, A. I.,Gitis, S. S.,Kaminskii, A. Ya.
, p. 1336 - 1343 (2007/10/02)
In the reaction of the glycol ethers of picric acid, containing 2-4 methylene units, with alkali-metal methoxides, tert-butoxides, and glycolates the intermolecular 1,1-?-complexes are formed in addition to the intamolecular spirocyclic anionic ? complexes.Thus, irrespective of the nature of the solvent and the nucleophilic agent, 1-(β-hydroxyethoxy)-2,4,6-trinitrobenzene undergoes intramolecular spirocyclization to a ? complex with a 1,3-dioxolane spirocycle.For 1-(δ-hydroxybutoxy)-2,4,6-trinitrobenzene only the formation of intermolecular 1-methoxy-1-hydroxyalkoxy- and 1,1-dihydroxyalkoxy-2,4,6-trinitrocyclohexa-2,5-dienides is observed, whereas 1-(γ-hydroxypropoxy)-2,4,6-trinitrobenzene can give ? complexes of both types, depending on the polarity of the solvent.
