3698-53-1Relevant academic research and scientific papers
Nitration of some di- and tri-nitrohalobenzenes with solid sodium nitrite in the presence of 18 crown 6
Badea, Florin,Stoica, Alice,Ioni?ǎ, Petre,Cǎproiu, Miron T.,Constantinescu, Titus
, p. 351 - 356 (2007/10/03)
1-Halo-4-R1-6-R2-2-nitrobenzenes 1a-d (where a : hal = F, R1 = NO2, R2=H; b: hal = Cl, R1 = NO2, R2 = H; c: hal = Cl, R1 = H, R2 = NO2 ; d: hal = Cl, R1 = CF3, R2 = NO2; ) and 1-chloro-2,4,6-trinitrobezene 1e were nitrated in methylene chloride with solid sodium nitrite in the presence of 18C6, and afforded the corresponding nitroderivatives 4-R1-6-R2-1,2-dinitrobenzenes 3a-c (where a: R1 = NO2, R2 = H; b: R1 = H, R2 = NO2; c: R1 = CF3, R2 = NO2; ) and 1,2,3,5-tetranitrobenzene 3d, respectively. The yields of this nucleophilic process depended on the number of nitro substituents and on the halogene type. UV-VIS and NMR spectra, TLC behaviour and pH-depending repartition in biphasic system water/methylene chloride of the synthecized compounds 3a-d are presented.
Synthesis of Polynitrobenzenes. Oxidation of Polynitroanilines and Their N-Hydroxy, N-Methoxy, and N-Acetyl Derivatives
Atkins, Ronald L.,Nielsen, Arnold T.,Bergens, Cynthia,Wilson, William S.
, p. 503 - 507 (2007/10/02)
Nitro-substituted arylhydroxylamines and alkyloxyamines have been oxidized to polynitroaryl compounds by utilizing ozone.Polynitroanilines have been oxidized to polynitroaromatics by peroxydisulfuric acid generated in situ from SO3 and ozone.Thus N-hydroxy-2,4,6-trinitroaniline (1a) or N-methoxy-2,4,6-trinitroaniline (1b) was cleanly oxidized to 1,2,3,5-tetranitrobenzene (2) by reaction with ozone in methylene chloride.Weakly basic amines such as pentanitroaniline (10) can conveniently be oxidized to hexanitrobenzene (11) in high yields by simply dissolving the amine in oleum and introducing ozone.A variety of substituted arylamines have been oxidized to polynitroaromatic compounds by using these two oxidation techniques.
Nitrocarbons. 4. Reaction of Polynitrobenzenes with Hydrogen Halides. Formation of Polynitrohalobenzenes
Nielsen, Arnold T.,Chafin, Andrew P.,Christian, Stephen L.
, p. 4575 - 4580 (2007/10/02)
Hexanitrobenzene and pentanitrobenzene in benzene solution react with hydrogen halides (HCl, HBr, HI, but not HF) at 25 deg C to produce high yields of pentanitrohalobenzenes and 2,3,4,6-tetranitrohalobenzenes, respectively.Pentanitrofluorobenzene also reacts readily with HCl to yield 3-chloro-2,4,5,6-tetranitrofluorobenzene, but the other pentanitrohalobenzenes are much less reactive. 1,2,3,5- and 1,2,4,5-tetranitrobenzenes react rapidly with concentrated hydrochloric or hydrobromic acids at reflux to form picryl halides and 1-halo-2,4,5-trinitrobenzenes, respectively; pentanitrotoluene reacts very slowly under these conditions to form 3-halo-2,4,5,6-tetranitrotoluenes in lower yields.The scope and limitations of this regioselective reaction are defined, and comparison is made to related reactions.A mechanism is presented and discussed.
Oxidation of Nitrobenzofuroxans
Boyer, Joseph H.,Huang, Chorngbao
, p. 365 - 366 (2007/10/02)
Monoperoxosulphuric acid oxidized 4-nitrobenzofuroxan into 1,2,3-trinitrobenzene (80percent) and 4,6-dinitrobenzofuroxan into 1,2,3,5-tetranitrobenzene (100percent).
AMBIPHILIC FUROXAN RING. BENZOFUROXAN OXIDATION BY PERACID AND REDUCTION BY COPPER
Boyer, Joseph H.,Huang, Chrongbao
, p. 1233 - 1240 (2007/10/02)
Monopersulfuric acid, trifluoroperacetic acid and hydrogen peroxide in polyphosphonic acid, or with selenium dioxide in t-butyl alcohol, or in tetramethylene sulfone have each oxidized benzofuroxan into o-dinitrobenzene.Monopersulfuric acid oxidized 4-nitrobenzofuroxan into 1,2,3-trinitrobenzene (80percent) and 4,6-dinitrobenzofuroxan into 1,2,3,5-tetranitrobenzene (99percent); hydrogen peroxide in polyphosphoric acid was moderately efficient for the latter oxidation.Copper in acidified ethanol transformed 4,6-dinitrobenzofuroxan into picramide quantitatively.
ACTION OF NITRIC ACID ON 2,4,6-TRINITROPHENYL ARENE AND ALKANECARBOTHIOATES
Nurgatin, V. V.,Sharnin, G. P.,Savel'eva, L. A.,Nurgatina, R. B.
, p. 2167 - 2169 (2007/10/02)
For the case of the reaction of S,S'-bis(2,4,6-trinitrophenyl)dithiooxalate with concentrated nitric acid it was found that the sulfur-containing groups in the esters of thiocarboxylic acids are substituted by hydroxy and nitroso groups.The reaction, which is accompanied by copious release of nitrogen oxides and increase in temperature, leads to 2,4,6-trinitrophenol or 2,4,6-trinitronitrosobenzene.The structure of the latter was confirmed by IR and UV spectroscopy and by oxidation to 1,2,3,5-tetranitrobenzene. 2,4,6-Trinitrophenyl benzenecarbothioates give the nitroderivative only when the acids contain not more than one nitro group in the phenyl radical.The nitroso group in 2,4,6-trinitronitrosobenzene, like the halogen in picryl halides, is readily substituted by the action of nucleophilic reagents.
Synthesis of Polynitro Compounds. Peroxydisulfuric Acid Oxidation of Polynitroarylamines to Polynitro Aromatics.
Nielsen, Arnold T.,Atkins, Ronald L.,Norris, William P.,Coon, Clifford L.,Sitzmann, Michael E.
, p. 2341 - 2347 (2007/10/02)
Peroxydisulfuric acid in sulfuric acid solution, prepared by reaction of hydrogen peroxide with excess oleum or 100percent H2SO4, oxidizes primary polynitroarylamines and their N-acetamido derivatives to polynitro aromatics in good to excellent yields.The new procedure is illustrated by the synthesis of several new polynitro compounds, not preparable by known synthetic methods.Peroxytrifluoromethanesulfonic acid is comparably efficient for such oxidations.The scope and limitations of the new reaction have been examined and compared to other methods of synthesis of polynitro compounds.
