Sodium nitrite-potassium ferricyanide

Marchand and co-workers reported a synthetic route to TNAZ (18) involving a novel electrophilic addition of NO+ NO2 across the highly strained C(3)-N bond of 3-(bromomethyl)-l-azabicyclo[1.1.0]butane (21), the latter prepared as a nonisolatable intermediate from the reaction of the bromide salt of tris(bromomethyl)methylamine (20) with aqueous sodium hydroxide under reduced pressure. The product of this reaction, A-nitroso-3-bromomethyl-3-nitroazetidine (22), is formed in 10% yield but is also accompanied by A-nitroso-3-bromomethyl-3-hydroxyazetidine as a by-product. Isolation of (22) from this mixture, followed by treatment with a solution of nitric acid in trifluoroacetic anhydride, leads to nitrolysis of the ferf-butyl group and yields (23). Treatment of (23) with sodium bicarbonate and sodium iodide in DMSO leads to hydrolysis of the bromomethyl group and the formation of (24). The synthesis of TNAZ (18) is completed by deformylation of (24), followed by oxidative nitration, both processes achieved in one pot with an alkaline solution of sodium nitrite, potassium ferricyanide and sodium persulfate. This route to TNAZ gives a low overall yield and is not suitable for large scale manufacture. 

Triketone (57), a key intermediate in the synthesis of 4,4,7,7,11,11-hexanitropentacyclo [6.3.0.0 .0 °.0 ]undecane (61) (Zlj-hexanitrotrishomocubane), has been synthesized independently by both Marchand and co-workers, and Fessner and Prinzach. Marchand and co-workers prepared the trioxime (58) from the corresponding triketone (57). Oxidation of (58) with peroxytrifluoroacetic acid in acetonitrile provides a direct route to the trinitro derivative (59) in 35 % yield, this yield reflecting an efficiency of 70 % for the oxidation of each oxime group. Subsequent oxidative nitration of (59) with sodium nitrite and potassium ferricyanide in aqueous sodium hydroxide yields the target T>3-hexanitrotrishomocubane (61). 

Paquette and co-workers synthesized the 5,11-dinitro isomer of 1,3-bishomopentaprismane (95) by treating the dioxime (94) with a buffered solution of m-CPBA in refluxing acetonitrile. A significant amount of lactone by-product (96) is formed during this step and may account for the low isolated yield of (95). Oxidative nitration of (95) with sodium nitrite and potassium ferricyanide in alkaline solution yields a mixture of isomeric trinitro derivatives, (97) and (98), in addition to the expected 5,5,11,11-tetranitro derivative (99), albeit in low yield. Incomplete reactant to product conversion in this reaction may result from the low solubility of either (97) or (98) in the reaction medium, and hence, incomplete formation of the intermediate nitronate anions. 

Olah and co-workers reported the synthesis of 2,2,5,5-tetranitronorbornane (127) from 2,5-norbornadiene (122). In this synthesis formylation of (122) with formic acid yields the diformate ester (123), which on treatment with chrominm trioxide in acetone yields 2,5-norbomadione (124). Formation of the dioxime (125) from 2,5-norbornadione (124) is followed by direct oxidation to 2,5-dinitronorbomane (126) with peroxytriflnoroacetic acid generated in situ from the reaction of 90 % hydrogen peroxide with TFAA. Oxidative nitration of 2,5-dinitronorbornane (126) with sodium nitrite and potassium ferricyanide in alkaline solution generates 2,2,5,5-tetranitronorbornane (127) in excellent yield. 

Potassium permanganate. Dimethyl sulfide-Chlorine. Dimethyl sulfoxide. Dimethyl sulfoxide-Chlorine. Dimethylsulf-oxide Sulfur trioxide. Dipyridine chro-mium(VI) oxide. Iodine. Iodine-Potassium iodide. Iodine tris(trifluoroacetate). Iodosobenzene diacetate. Isoamyl nitrite. Lead tetraacetate. Manganese dioxide. Mercuric acetate. Mercuric oxide. Osmium tetroxide—Potassium chlorate. Ozone. Periodic acid. Pertrifluoroacetic acid. Potassium ferrate. Potassium ferricyanide. Potassium nitrosodisulfonate. Ruthenium tetroxide. Selenium dioxide. Silver carbonate. Silver carbonate-Celite. Silver nitrate. Silver oxide. Silver(II) oxide. Sodium hypochlorite. Sulfur trioxide. Thalli-um(III) nitrate. Thallium sulfate. Thalli-um(III) trifluoroacetate. Triphenyl phosphite ozonide. Triphenylphosphine dibromide. Trityl fluoroborate. 

POTASSIUM FERRICYANATE, POTASSIUM FERRICYANIDE, or POTASSIUM HEXACYANOFERRATE(IH) (13746-66-2) Mixtures with water, acids, alcohols cause slow decomposition, producing hydrocyanic acid. Explosive reaction with ammonia. Violent reaction with copp)er(II) nitrate, trihydrate. Incompatible with chromium trioxide, sodium nitrite. 

In the early oxidation nitration preparation of DNPOH, the yield is relatively low (59-63 %), the product needs further purification, there is formaldehyde condensation reaction and other serious problems. Jeong et al. [63] modified the oxidation nitration process to optimize the oxidation nitration conditions of silver nitrate, in which aqueous formaldehyde solution (mass fraction of 35 %) was used for hy-droxymethylation and its reaction conditions were optimized, and a yellow solid DNPOH was obtained after extraction with methylene chloride and distillation. The average yield of DNPOH was more than 90 % and the mass fraction was more than 97 %. Based on these results, Grakauskas et al. [40-42, 65] used potassium ferri-cyanide as catalyst and potassium persulfate as oxidant to synthesize DNPOH. In this method, with potassium(sodium) ferricyanide and over potassium(sodium) persulfate, nitrite substitution reaction of nitroethane with sodium nitrite occurred, and then further reacted with formaldehyde under basic conditions, and finally DNPOH was extracted out with ethyl acetate under acidic conditions. Product was obtained through potassium distillation. The reaction mechanism is ... 

In the improvement of DNPDOH (2,2-dinitro-1,3-propanediol) [66], used sodium nitrite was reduced from 4 times to the equal amount, the amounts of sodium persulfate and potassium ferricyanide were adjusted, which reduced the impact of carbon emission pollution on the environment, and the cost of synthesis was reduced. The synthesis yield was 68 % after improvement, and lower than the production cost is much lower than that of silver nitration method. Major improvement in electrochemical synthesis of DNPOH is that In the first step, sodium hydroxide solution was added to an aqueous solution of 2-nitropropanol after 45 min of stirring at room temperature, lithium perchlorate solution and sodium nitrite solution were added to prepare the deprotonated 2-nitropropanol solution in the second step, deprotonated 2-nitro-propanol solution is added into the working electrode chamber and the reference electrode chamber of the electrolytic cell, and electrolytic reaction is continued for about 1 h under nitrogen for 20 min. Finally DNPOH will be obtained with a yield of about 40 %. The reaction mechanism is ... 

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