Reaction with Tetranitromethane

Tetranitromethane (TNM) (194) has been used in protein chemistry for the selective chemical modification of tyrosine residues 367). It was 

CuATRECASAS et al. (92) observed that TNM can cause nitration of the single tryptophan residue in staphylococcal nuclease, but the nature of the nitro derivative was not determined. The inactivation of papain by TNM has also been thought to be due to tryptophan modification 264). Nitration has been observed also with lactoferritin 407). 

Sokolovsky et al. 368) studied the reaction of TNM with amino acids other than tyrosine and found that cysteine, methionine, histidine and tryptophan could be modified by the reagent. By using tryptophan model compounds, it was demonstrated that a number of nitrated derivatives of tryptophan of unknown structure could be obtained. 

Spande, Fontana and Witkop 370) studied the reaction of TNM with the model compound skatole. When this compound was allowed to react with TNM in ethyl ether, a yellow compound was isolated whose structure was shown to be the 2-dinitromethylene-3-nitro derivative (197). A rationale for the formation of (197) is illustrated by the sequence (195)- (197). Reduction of (197) with excess Na2S204 led to 2-cyano-3-methylindole (198). 

It must be emphasized that the dinitromethylene compound was obtained when the reaction was carried out in an organic solvent. The usual nitration conditions with TNM in aqueous buffers could lead to an alternate reaction pathway. 

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Even simple dienes and polyenes are difficult to classify in comparison with alkenes. Whereas bromination, oxidation and reaction with tetranitromethane (TNM) can identify the number of double bonds and their location in the molecular structure, conjugated double bonds produce very complex mixtures. Furthermore, many of the tests based on 7r-complexation can also apply for aromatic moieties. An example is the TNM 7r-complex which is yellow with benzene and orange with naphthalene and the tests are therefore non-specific. 

As illustrated in Equation (77), the regioselective nitration of 2-(trimethylstannyl)benzo[/)]furan was also applied to the synthesis of 2-nitrobenzo[ ]furan. The reaction proceeded by an initial treatment of benzo[ ]furan 82 with -BuLi/ MesSnCl, and was then followed by reaction with tetranitromethane (TNM) or dinitrogen tetroxide <2003EJ01711>. 

Treatment of thietane with electron acceptors, such as tetracyanoquino-dimethane (TCNQ), tetracyanoethylene (TCNE), maleic anhydride, or tetra-nitromethane, induces polymerization, believed to occur through an intermediate charge-transfer complex. The reaction with tetranitromethane is unusual because nitric oxide, nitrogen dioxide, carbon monoxide, ethylene, ethane, and propane are... 

HAZARD RISK Very dangerous fire hazard explodes in vapor form when exposed to heat or flame explosive reactions with tetranitromethane, nitric acid and sulfuric acid reacts violently with oxidizers NFPA Code H 2 F 3 R 0. 

Figure 4.21 Tyrosine reactive probes. Nitration of tyrosine by reaction with tetranitromethane, followed by reduction with sodium dithionite, to yield an o-aminotyrosine.

Reaction with tetranitromethane gave the nitrostyrene intermediate which had a mp of 120-121 deg C. The final hydrochloride salt of EMDA-2 had a mp of 188-188.5 deg C. At 135 milligrams, there have been reported eyes-closed visual phenomena, with intense colors. The overall duration is similar to MMDA-2 (some 10 hours) and there are reported sleep disturbances. At 185 milligrams, the feelings were intensified, there were "marvelous eyes-closed visuals (the colors were incredible), good concentration, but distinct body-tingles and... 

This intermediate, produced by action of alkali on tetranitromethane, must be kept damp and used as soon as possible with great care, as it may be explosive [1], Material produced as a by-product in a nitration reaction using tetranitromethane was washed with acetone. It exploded very violently after several months storage [2],... 

Nitroisoxazolines were prepared from ALalkoxy-3,3-dinitroisoxazolidines by thermally induced P-elimination. For example, isoxazolidines 42 synthesized by a three-component reaction of tetranitromethane with two equivalents of alkenes 41, were converted into isoxazolines 43 by heating in boiling chlorobenzene <06S706>. 

Equally interesting processes occur in the reactions of tetranitromethane and some of its derivatives with olefins (Scheme 3.10). 

The oxidative behaviour of glycolaldehyde towards hexacyanoferrate(III) in alkaline media has been investigated and a mechanism proposed, which involves an intermediate alkoxide ion. Reactions of tetranitromethane with the luminol and luminol-peroxide radical anions have been shown to contribute substantially to the tetranitromethane reduction in luminol oxidation with hexacyanoferrate(III) in aerated aqueous alkali solutions. The retarding effect of crown ethers on the oxidation of triethylamine by hexacyanoferrate(III) ion has been noted. The influence of ionic strength on the rate constant of oxidation of ascorbic acid by hexacyanofer-rate(III) in acidic media has been investigated. The oxidations of CH2=CHX (where X = CN, CONH2, and C02 ) by alkaline hexacyanoferrate(III) to diols have been studied. ... 

Nitration with tetranitromethane proceeds along the ion-radical ronte. Tetranitromethane is a smooth nitrating agent and mild oxidizer. It is convenient for nitration of highly activated snbstrates snch as phenols, azulene, and heterocycles in the presence of pyridine, N,iV-dialkylaniline, etc. As shown (Morkovnik 1988), these reactions inclnde one-electron transfer ... 

Studies of interactions between tetranitromethane and aryl derivatives of magnesium, tin, and mercury in sulfolane (Shevelyov et al. 1974, 1975) confirm that NO2 radical has some slight activity. For example, the reaction of diarylmercury with tetranitromethane passes through a transient step with the formation of radicals Ar and NO2. These radicals almost do not interact ... 

Nielsen and Bedford synthesized gem-dinitroalkanes (147) from the Michael addition of organolithium reagents to a-nitroalkenes (146) followed by quenching of the resulting nitronate anion with tetranitromethane. The same reaction using alkoxides as bases provides P-alkoxy-gem-dinitroalkanes (148). ... 

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