1.3.5- Trinitrobenzene, reaction with potassium

Reaction of 1,3,5-trinitrobenzene (TNB) with o-aminophenols in the presence of potassium carbonate in dipolar aprotic solvents has been shown to produce 1,3-dinitrophenoxazines (5). This reaction is thought to involve nitro group displacement to yield intermediates (4), which undergo oxidative substitution of hydrogen by the amino group.18 The corresponding reaction of TNB with o-aminothiophenols yields 1,3-dinitrophenothiazine derivatives. 

Oxidation of nitro compounds to nitrophenols is another example of a nucleophilic reaction. Thus, m- dinitrobenzene and sym- trinitrobenzene were oxidized in an alkaline medium when boiled with potassium ferricyanide solution (Hepp[45]) ... 

As early as 1895 Lobry de Bruin [22] described a red solid which he isolated m the reaction of 13>5-trinitrobenzene with potassium hydroxide in methanol. [Ileyer [23] suggested this to be a complex compound. Hantzsch and Kissel ) rationalized that the complex might be a potassium salt of aci-form of one group. Jackson and Gazzolo [25] suggested in 1900 two structural formulae the sodium salt obtained by acting with sodium methoxide on 2,4,6-trinitro-il Fig. 1 Sa. Meisenheimer [26] (probably unaware of Jackson s paper)... 

ESTANO (Spanish) (7440-31-5) Finely divided material is combustible and forms explosive mixture with air. Contact with moisture in air forms tin dioxide. Violent reaction with strong acids, strong oxidizers, ammonium perchlorate, ammonium nitrate, bis-o-azido benzoyl peroxide, bromates, bromine, bromine pentafluoride, bromine trifluoride, bromine azide, cadmium, carbon tetrachloride, chlorine, chlorine monofluoride, chlorine nitrate, chlorine pentafluoride, chlorites, copper(II) nitrate, fluorine, hydriodic acid, dimethylarsinic acid, ni-trosyl fluoride, oxygen difluoride, perchlorates, perchloroethylene, potassium dioxide, phosphorus pentoxide, sulfur, sulfur dichloride. Reacts with alkalis, forming flammable hydrogen gas. Incompatible with arsenic compounds, azochloramide, benzene diazonium-4-sulfonate, benzyl chloride, chloric acid, cobalt chloride, copper oxide, 3,3 -dichloro-4,4 -diamin-odiphenylmethane, hexafluorobenzene, hydrazinium nitrate, glicidol, iodine heptafluoride, iodine monochloride, iodine pentafluoride, lead monoxide, mercuric oxide, nitryl fluoride, peroxyformic acid, phosphorus, phosphorus trichloride, tellurium, turpentine, sodium acetylide, sodium peroxide, titanium dioxide. Contact with acetaldehyde may cause polymerization. May form explosive compounds with hexachloroethane, pentachloroethane, picric acid, potassium iodate, potassium peroxide, 2,4,6-trinitrobenzene-1,3,5-triol. 

Crude enzyme was assayed in a final volume of 0.1 mL using 25 mM DKP, 25 mM potassium phosphate buffer, pH 8.0, and 1.25 mM EGTA. Reactions were started with enzyme and incubated for 30 minutes at 30°C. The reaction product, a-AP, was quantitated by HPLC after reaction with phenyl isothiocyanate (PITC). Another spectrophotometric assay used throughout the purification was carried out by measuring a-AP with trinitrobenzene sulfonate (TNBS) after incubation at pH 8.0 and 50°C using the above substrate and buffer concentrations. One unit of enzyme activity is defined as 1 pmol a-AP produced/min at pH 8.0 and 50°C using an 6416 of... 

It has been extended to other ketones. Sometime later, it was discovered that this reaction is positive with molecules possessing an active methylene, such as a-methylene ketones. Zimmermann applied it to 17-ketosteroids of great pharmacological interest. Numerous experimental modifications have been proposed, including the use of organic bases instead of potassium hydroxide and the use of other nitro derivatives of benzene. It seems well established that when m-dinitro or 1,3,5-trinitrobenzene reacts with an excess of a compound possessing an active methylene in basic medium, a o Meisenheimer complex forms ... 

Electrochemical oxidation of the anionic o -complexes derived from the reaction of 1,3,5-trinitrobenzene with phosphorus nucleophiles proved to be an effective way to the corresponding Sn products. For instance, the reaction of TNB with dimethyl phosphonate takes place easily in DMF at room temperature in the presence of potassium ieri-butoxide under argon atmosphere to give the target dimethyl (2,4,6-trinitrophenyl) phosphonate in 80% yield (Scheme 60) [164]. 

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