Tetranitro derivatives

Attempts to prepare hydroxybiphenyl derivative 19 by treatment of tetranitro derivative 18 with sodium benzaldoxime led to a mixture of the required phenol 19 and dibenzofuran 20 (Eq. 5) (82JCS(P1)2299). 

Denitrocyclization reaction was also used for the preparation of hexacyclic derivative 278, which was obtained in 80% yield by heating of 277 with a solution of sodium hydroxide in aqueous DMF (66JCS(C)1245, 70JCS(C)2647). Low to moderate yields of 3,6-dinitroxanthen-9-one (281) is formed by a treatment of tetranitro derivative 279 with either potassium hydroxide or sodium... 

Much more promising is the method of Schechter and Haller (3), which depends upon the coupling of the tetranitro derivative of DDT with methanolic sodium methylate. Under conditions of intensive nitration methoxychlor will yield by this procedure a red color with an absorption maximum at 535 m/z. 

Nitration of the diazido dinitro derivative 81 proceeds easily to give the 4,8-diazido-2,3,9,10-tetranitro derivative 82 in 76% yield (Equation 3). The ease of the nitration of 81 stems from activation of the C-3 and C-9 positions toward electrophilic attack by the ortho-directing effect of the azido groups <1996JOC5801>. 

Tetranitro derivative 90 (z-TACOT Section 12.10.15.5) treated with methanolic sodium methoxide at ambient temperature does not lead to simple product of nucleophilic substitution of a nitro group but provides compound 92. Its formation can be rationalized by introduction of the methoxy group into the 1-position, followed by scission of the remote triazole ring of 91 to give the final product. Compound 90 subjected to the vicarious nucleophilic substitution (VNS) conditions using either hydroxylamine or trimethylhydrazinium iodide gives a very insoluble red solid, which was identified as l,3,7,9-tetraamino-2,4,8,10-tetranitrobenzotriazolo[2,l- ]benzotriazole 93 (Scheme 5) <1998JOC3352>. 

Tetranitro derivative 94 (y-TACOT Section 12.10.15.5) treated with sodium azide in DMSO gives 83% yield of a single symmetrical diazido dinitro derivative 81 resulting from nucleophilic substitution of an equivalent pair of nitro groups by the azide anion (Equation 5) <1996JOC5801>. 

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. 

The dipyridotetraazapentalene ring (236) also exhibits high thermal stability. The tetranitro-derivative of this ring system, aza-TACOT (237), is synthesized by a similar route to that of y-TACOT, but is more energetic than the latter. " °... 

Chloro-4, 5-dinitrobiphenyl has been prepd by the mixed acid nitration of 2-chlorobiphenyl, mp 159°, further nitration may yield small amts of a tetranitro deriv melting at 127°... 

See Aminohydroxyanthraquinone and Derivatives in Vol 1 of Encycl, p A217-L. Its Tetranitro-derivative (Aminochrysammic Acid), described on p A217-L, forms expl salts of Ammonium, Barium and Potassium... 

Also called 2,6-Dinitro-4-Picrylaminephenol in Ger). (O, N)3C6H2NHC6H2(N02)20H mw 410.22, N 20.49%, OB to C02 -62.4% ochre-yel crystals (from HAc), mp 248° insol in water, si sol in ale sol in alkalis with formation of a deep-brown color. Prepd by heating picryl chloride, isopicraminic acid NaAc in aq ale. No explosive props are mentioned for it nor for the tetranitro derivatives (Ref 2). The Na salt, of the pentanitro derivative NaCi2HsOuN6, red platelets, explodes above 300°. The 3 -Hydroxy-4-methyl-pentanitro diphenylamine is not explosive (Ref 3)... 

Although no later refs are found in CA thru 1971 for mono thru tetranitro derivs, the di-nitrocompd was prepd forNDRC by R.L. 

The purification of tetryl aims at removing by-products such as tetranitro derivative (VII), substances insoluble in benzene and the spent acid occluded by the crystals. The product is washed with cold water and then treated with hot water. This brings about the conversion of compound (VII) to (VIII)—the latter is soluble in hot water. The tetryl is then dissolved in benzene and insoluble constituents removed by filtration. The resulting solution is washed with water until it is completely free from acid. Alternatively, tetryl may be dissolved in acetone, precipitated with water, and finally deacidified. 

Diacetylaminophenol, C10HJ4NO3, may be considered as the parent compd of its tetranitro deriv but is not used to prepare it X-Tetranitrodiacetylcminopbenol, (02N)4-< (OH).N(OC.CH3)2 raw 373=56, N 18.85% col short ndls (from benz or peer ech), mp 147 47.5 was obtd when benzene-free pent an itro aniline was boiled with acetic anhydride two drops of H2SO 4, followed by cooling, removing the excess anhydride, and mixing with snow (Refs 1 2)... 

No expl props of the tetranitro derivs were reported... 

The expl props of the tetranitro derivs were not reported. Yamasiro (Refs 6 7) also prepd 2,3,5,7- 2,4,6,8- and 1,3,7,8-tetranitro derivs... 

Dibenzotetrazapentalene, Ci2HgN4, may be considered as the parent compd of its tetranitro deriv ... 

C6H2(N02)2-N(N02).CH2CH(CH3)2]2 mw 566.44, N 19.78% ndls (from coned HNO3), mp-dec at 205° obtd from the tetranitro deriv by treating with coned HNOj (Refs 1 2)... 

N 21.97% lt-yel ndls (from HNOj), mp 230° (dec) was prepd by treating the tetranitro deriv with coned HNO3 (Ref 2). No expl props were detd... 

NOTE See also Diethylbiphenyldiamine and its Tetranitro Derivatives in this Vol... 

Oimetbylbenzophenone, CigHj40, mw 210.26. Several isomers are known, but only one has been nitrated to form a tetranitro deriv ... 

N 18.18% flakes, mp - not reported readily sol in ale si sol in acet ac insol in ether, cumol nitrobenzene prepd by nitrating the tetranitro deriv with an excess of fuming nitric acid (Ref 3)... 

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