Chlorobenzene 2,4,6-trinitro

Dinitro-chlorobenzene 2,4,6-Trinitro-chlorobenzene (picryl chloride) Vinyl chloride Vinyl bromide... 

Other examples of oxynitration include the formation of (1) 2,4,6-trinitro-m-cresol from toluene, (2) 2,4-dinitronaphth-l-ol from naphthalene, (3) 3-chloro-2,4,6-trinitrophenol from chlorobenzene and (4) 3-hydroxy-2,4,6-trinitrobenzoic acid from benzoic acid. ... 

Commercial DNCB, yel crysts, mp ca 5 0°, consists mostly of 2,4-DNCB with a small amt of 2,6-DNCB. This product is considered more toxic than NB. It causes dermatitus systemic poisoning(Ref 12). DNCB is an expl si more powerful than DNB and comparable in sensitivity to TNT(Ref 4). The expl props of DNCB its mixts with PA, TNT or AN were studied by Burlot Tavernier(Ref 7). It has been reported that phosgene is produced on low order deton of DNCB(Ref 6). DNCB is used as an intermediate in one method for the manuf of tetryl. It may also be further nitrated to 2, 4,6 -Trinitro-l-chlorobenzene(abbreviated TNCB) and also known as Picryl Chloride(See below) Refs l)Beil 5, 262-64, (137-39) [196-97] 2)G.Koerner A. Contardi, AttiAccadLincei-Rend 23, 4 64-71(1914) SS 10, 77(1915) 2a) Ullmann 2(1928), 277-78 3)J. Mason, JCS... 

Trinitro-4 -chlorobenzene, yel ndls(from ale), mp 68-9° can be prepd by heating 1,2 -dinitro-4-chlorobenzene with fuming nitric acid and oleum. Its expl props were not detd (Ref 1 Ref 2,p 613)... 

Trinitro-5 -chlorobenzene, yel crysts(from benz), mp 168° can be prepd by treating 2,6 -dinitro-4-chloro-1-benzene diazonium nitrate with Cu sulfate and Na nitrite in w. Its expl props were not detd... 

Trinitro-5 -chlorobenzene, yel-crysts (from ale), mp 116° can be prepd by treating 5 -chi oro-2,4 -dinitro- 1-ben Zen edi azonium nitrate with Na nitrite in w or by other methods. 

Trinitro-3-chlorophenol or Chloropicric Acid, yel crysts(AcOH or ale) or prisms(from w), mp 112-19°, not volatile with steam mod sol in chlf, benz, ale or eth can be obtd as the ultimate product of nitration of all mono- di-nitro-3-chlorophenols (Refs 2 3). It forms yel salts of Na, Ag, NH3 (mp 223 24 °) PhNH2 (mp 189 90°). See Refs 2, 3, 5,6, 7 8 for other props methods of prepn. The Chloride salt, an expl compd called Chloropicryl Chloride, is mentioned under Trinitrochloro-benzenes, Derivatives of Chlorobenzene... 

The. nitration of m-dinitrobenzene is too expensive of acid and of heat for practical application, and the yields are poor. Toluene and chlorobenzene are nitrated more easily and more economically, and their trinitro compounds are feasible materials for the preparation of TNB. Oxidation with nitrosulfuric acid has obvious disadvantages. The quickest, most convenient, and cheapest method is probably that in which TNT is oxidized by means of chromic acid in sulfuric acid solution. 

The nitration of chlorobenzene is easier than the nitration of benzene and more difficult than the nitration of toluene. Trinitro-chlorobenzene (picryl chloride) can be prepared on the plant scale by the nitration of dinitrochlorobenzene, but the process is expensive of acid and leads to but few valuable explosives which cannot be procured more cheaply and more simply from dinitrochlorobenzene by other processes. Indeed, there are only two important explosives, namely TNB and hexanitrobiphenyl, for the preparation of which picryl chloride could be used advantageously if it were available in large amounts. In the laboratory, picryl chloride is best prepared by the action of phosphorus pentachloride on picric acid. 

Davis and his co-workers [127,128] found chlorobenzene also undergoes oxynitration by action of 65% nitric acid, with formation of trinitro-m-chlorophenol along with chlo-ronitrobenzenes, while naphthalene when nitrated with more dilute acid, for example, at a concentration of 65%, yielded 2,4-dinitro-a-naphthol besides 2-nitro-a-naphthol. 

The following diagram represents the complete process of nitration of chlorobenzene to trinitro derivatives ... 

Gaseous products which accompany the nitration are CO and 00. Toluene on nitration to trinitro derivative forms tetranitromethane (the mechanism of its formation is given in the chapter dedicated to the production of trinitrotoluene). Chlorobenzene and other chlorinated aromatic hydrocarbons yield chloropicrin. 

Aromatic substitution reactions usually occur by an electrophilic mechanis Ary halides that have electron-withdrawing substituents, however, can also undergo nucleophilic aromatic substitution. For example, 2,4,6-trinitro-chlorobenzene reacts with aqueous NaOH at room temperature to give 2,4,6-trinitrophenol in 100% yield. The nucleophile OH has substituted for Cl". 

Watanabe T, Ishihara N, Ikeda M. 1976. Toxicity of and biological monitoring for 1,3-diamino-2,4,6-trinitro-benzene and other nitro-amino derivatives of benzene and chlorobenzene. Int Arch Occup Environ Health 37 157-168. 

Trinitro derivatives of chlorobenzene Picryl chloride Physical properties Chemical properties l-Chloro 2,4.5-trinitrobenzene Diagram of the nitration of chlorobenzene Thermochemical and explosive properties of chloronitrobenzenes Nitro derivatives of p-chlorobenzene Mononitro derivative of p-chlorobenzene Dinitro derivative ofp-dichlorobenzene 2,4,6-Trinilroderivativc of L3.5-trichlorobcnzene Manufacture of L3,5-lrichloro-2.4,6-irinitrobenzene Nitro derivatives of fluorobenzene Literature... 

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