1.3- Dichloro-4,6-dinitrobenzene, reaction

A,A -Bis(3-aminopicryl)-l,2-ethanediamine (108) (m.p. 275 °C) is prepared from the reaction of ethylenediamine with two equivalents of 3-chloro-2,4,6-trinitroaniline. " The same chemists reported 3,3 -diamino-2,2 4,4, 6,6 -hexanitrodiphenylamine (109), a heat resistant explosive (m.p. 232-237 °C) prepared from the reaction of l,3-dichloro-4,6-dinitrobenzene with 3-chloroaniline followed by mixed acid nitration and subsequent chloro group displacement with ammonia. The potassium salt of 3,3 -diamino-2,2, 4,4, 6,6 -hexanitrodiphenylamine shows very high thermal stability. " ... 

Similar routes have been used for the synthesis of other polynitrophenylenes. 1,3,5-Tris(2,4,6-trinitrophenyl)-2,4,6-trinitrobenzene (160) is synthesized from the reaction of 1,3,5-trichloro-2,4,6-trinitrobenzene with three equivalents of picryl chloride in the presence of activated copper powder in refluxing mesitylene. " 2,2",4,4, 4",6,6, 6"-Octanitro-m-terphenyl (161) has been synthesized from picryl chloride and l,3-dichloro-4,6-dinitrobenzene. ... 

Pagoria and co-workers synthesized a number of thermally stable explosives from the reaction of the sodium salt of ANTA with chloro-substituted arylenes and A-heterocycles. These include the synthesis of (117) from picryl ehloride, PRAN (118) from 2-chloro-3,5-dinitropyridine, IHNX (119) from 2,4-dichloro-5-nitropyrimidine, (120) from 1,5-dichloro-2,4-dinitrobenzene, and (121) from 4-chloro-6-(3-nitro-l,2,4-triazolyl)-5-nitropyrimidine. Coburn and co-workers " reported the synthesis of the tetrazine (122) and the triazine (123) from the reaction of the sodium salt of ANTA with 3,6-dichlorotetrazine and cyanuric chloride respectively. 

The nitration of l,3,5-trichloro-2-nitrobenzene (8) to l,3,5-trichloro-2,4-dinitrobenzene (9) with dinitrogen pentoxide in absolute nitric acid goes to completion in only 2-4 minutes at 32-35 °C. Further nitration of (9) would yield l,3,5-trichloro-2,4,6-trinitrobenzene (10) which undergoes ammonolysis on treatment with ammonia in toluene to give the thermally stable explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) (11). The same sequence of reactions with l,3-dichloro-2-nitrobenzene provides a route to l,3-diamino-2,4,6-trinitrobenzene (DATE). Such reactions are clean and occur in essentially quantitative yield. 

Nitronium tetraHuoroborate and m dinitrobenzene were added to fluoro-sulphuric acid and cooled in a dry ice/acetone bath. The temperature was gradually raised to ISO C. After three hours of heating the reaction mixture was poured on to crushed ice. The nitro product was extracted with dichloro-methane, washed with sodium hydrogen carbonate solution and dried over magnesium sulphate. The yield of sym-trinitrobenzene was 61.6% with 5% unreacted m-dinitrobenzene. 

Irradiation at 350 nm of 1,1-dibromocyclopropanes dissolved in liquid ammonia or dimethyl sulfoxide in the presence of sodium benzenesulfanate leads to l,l-bis(phenylsulfanyl)cyclo-propanes. The yields are in all cases below 50% which is due to both decomposition of the product on longer irradiation and formation of significant amounts of cyclopropyl phenyl sulfide. Most 1,1-dichlorocyclopropanes are unreactive, and no reaction occurs in the presence of oxygen, di- erf-butyl nitroxide and 1,3-dinitrobenzene, which supports the notion that the reaction is a radical process. The cleanest reaction took place during irradiation of 2,2-dichloro-1 -methylcyclopropanecarbonitrile, which gave no sulfide, little unreacted starting material, and 1-methyl-2,2-bis(phenylsulfanyl)cyclopropanecarbonitrile (4) in 47% yield. 

Fig. 2. Metabolism of model substrates by GST. The following reactions are catalyzed by GST (a) f-chloro-2,4-dinitrobenzene, (b) l,2-dichloro-4-nitrobenzene, (c)r/-a>w-4-phenyl-3-buten-2-one, (d) ethacrynic acid, (e) l,2-epoxy-3-(p-nitrophenoxy)propane, and (f) menaphthyl sulfate.

The glutathione 5-transferases catalyze numerous reactions in which the glutathione thiolate anion (GS ) serves as a nucleophile (A20, G11, J2). Thus the fundamental catalytic action of GST is to facilitate the formation or stabilization of GS , which can, in turn, attack electrophilic carbon, nitrogen, sulfur, or oxygen atoms contained in any xenobiotic. Literally hundreds of different compounds exist that contain a carbon atom sufficiently electrophilic to be able to react with GS" and form thioether conjugates. Thioether formation has been widely studied since the earliest convenient spectrophotmetric assays represented this type of reaction for example, the conjugation of GSH with l-chloro-2,4-dinitrobenzene, 1,2-dichloro-... 

Two examples may be given, by reacting the reduced form of Nile Blue with 1,5-dichloro-2,5-dinitrobenzene, one compound could be obtained with an E -value of —135 mV vs SCE (pH 7.0), and by reacting the iminoform of Brilliant Cresyl Blue with terephthaloyl chloride a compound could be obtained with an E -value of —55 mV vs SCE (pH 7.0). They were both found to be catalytically active for NADH-oxidation. No kinetic data are available yet, however. Purification and identification of both the commercially available phenoxazines (usually with a purity of 50-90 %) and of the reaction products are far from straightforward. 

The reaction of l,2-dichloro-4,5-dinitrobenzene with dilute aqueous sodium hydroxide results in substitution of a nitro-group by hydroxide. However, in hydroxide concentrations greater than 2 mol-dm", only the formation of monohydroxy- and dihydroxy-adducts (42) is observed, and acidification yields the original reactant. The cyanide adduct (43) of 1,3,5-trinitrobenzene has been observed by electrospray ionization mass spectrometry, using acetonitrile as the cyanide source. X-ray structures of the stable crystalline adducts formed from 4,6-dinitrobenzofiiroxan and dodecyl- and hexadecyl-amine have been reported. There has also been a report, related to the destruction of energetic materials, of Meisenheimer complex formation during the alkaline hydrolysis of 2,4,6-trinitrotoluene and 2,4-dinitroanisole. ... 

OxacaUx[4]arenes were first synthesized in 1966 by Sommer and Staab by nucleophilic aromatic substitution (S Ar) reaction of resorcinol 2a and l,5-dichloro-2,4-dinitrobenzene 3 using K2CO3 base in DMF (Scheme 15.1) [6]. A 13 % yield of the... 

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