Jackson-Meisenheimer complex

F. Terrier, Rate and Equilibrium Studies in Jackson Meisenheimer Complexes, Chem. Rev., 82 (1982) 77. 

Jackson-Meisenheimer complexes can serve in obtaining nitro derivatives of diphenyl. An original approach to this type of reaction was given by Wenner-ttrom [52]. He reacted a derivative of phenylsUver with 1,3,5-trinitrobenzene in the presence of pyridine. The oxidation of the o-complex yielded compound VI. 

Pyfe. Malkiewich and Norris [ >41 examined intermediates formed by the action of bases on TNT using high resolution NMR spectroscopy. Wiilmi 0 5 sec of mixing equimolar proportions of TNT and methoxide in l)S() and t lliOII the Jackson Meisenheimer complex is formed. It decayed over S sec and ilie 1 spectrum of anion according to (5) slowly appeared. 

Naphthalene analogues of Jackson-Meisenheimer complexes were described [28, 42] and 9-anthracene derivative has already been discussed by Meisen-heimer [26]. 

A few heterocyclic Jackson-Meisenheimer complexes were recorded, viz. I [29] II [30]. Vickery [31a] rationalized the structure of the complex (HI) obtained in 1883 by Lobry de Bruin [31b] while acting with potassium cyanide on m-dinitrobenzene. 

The reaction of l,3,S-trinitroben2ene with diazomethane was carried out as early as 1898-1900 [88, 89), but only recently de Boer rationalized it as a nucleophilic addition leading to seven member ring condensed with two cyclopropane rings when the molar ratio of trinitrobenzene to diazomethane was 1 3. The first step of the reaction was a type of Jackson-Meisenheimer complex (Ai) and the final product was trismethylene-trinitrobenzene (A ) [90—92a] (19). The reaction is temperature dependent at —80 C compound (A ) was formed. 

Addition of nucleophiles to aromatic compounds with several nitro or cyano groups leads to the formation of a resonance-stabilized carbanion known as a Jackson-Meisenheimer complex. For example, addition of sulfite ion to 1,3,5-trinitrobenzene leads to the complex 4 (Figure 3.5). 

Although this type of structure was first reported by Jackson et al. in 1900 for the reaction between picryl ether and potassium alkoxide, it was Meisenheimer who actually isolated and characterized the structure of such molecule for the first time in 1902. Since then, the stable or transient anionic a complexes formed from electron-deficient aromatic compounds and a variety of organic and inorganic bases" are generally called the Meisenheimer complexes. Occasionally, this type of molecule is also referred to as the Meisenheimer adducts, Meisenheimer compounds, Meisenheimer cr-adducts, Meisenheimer a complexes, Jackson-Meisenheimer adducts, or Jackson-Meisenheimer complexes. ... 

The kinetics of nucleophilic aromatic substitution is almost always second order—first order in nucleophile and first-order in the aromatic electrophile. The intermediate structure is called the Meisenheimer complex (or Jackson-Meisenheimer complex). The Meisenheimer complex can sometimes be directly observed at low temperatures. In aprotic sol-... 

Meisenheimer complex (Meisenheimer-Jackson salt) Example... 

Highly-colored Jackson-Meisenheimer,or a, complexes of structure II or III are formed by addition to the ring system. The controversial history of the study of these compds has been well reviewed (Refs 44,46,51,70 82). They are formed in aq and anhydrous medium, and with a variety of organic and inorganic nucleophiles. Most of these studies have been made with 1,3,5 -trinitrobenzene rather than TNT, since the absence of a reactive methyl group in the former simplifies product isolation and identification. 

Electrophilic substitution Nucleophilic addition and substitution Nucleophilic displacement of nitro groups Jackson-Meisenheimer reaction and complexes Practical significance and application of Jackson-Meisenheimer reaction Reaction potential map(RPM)... 

Jackson-Meisenheimer type complexes can become intermediates which are [Airther transformed into products of nucleophilic attack. Bowie 47] has produced diagrams as follows ... 

Jackson-Meisenheimer compounds are now recognized as a-complexes. Currently their mode of writing is given in Fig. 15b, and the formation presented in diagram (1) ... 

Meisenheimer adduct A cyclohexadienyl derivative formed as Fewis adduct from a nucleophile (Fewis base) and an AROMATIC or heteroaromatic compound, also called Jackson-Meisenheimer adduct. In earlier usage the term Meisenheimer complex was restricted to the typical Meisenheimer alkoxide adducts of nitro-substituted aromatic ethers, for example... 

FIG 15. Jackson-Meisenheimer o complexes (a) former, (b) current method... 

Murto (14) examined the action of sodium ethoxide on 1,2,3,5-tetranitro-benzene. It produced a red colour attributed to the formation of a quinoid structure and eventually sodium picrate. A more detailed study of the action of nucleophiles on 1,2,3,5-teiranitrobenzene was made by Crampton and tl Ghari-ani [15. They obtained a-complexes of Jackson—Meisenheimer type. 

Jackson-Meisenheimer rr-complexes see Meiscnhcimcr o-complcxes Jackson-Meiscnhcimcr reaction ee Meiscnhcimcr reaction Jdnovskv reaction 96. 103 (I 207. 20s. 

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)... 

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