The acetoxylation of arenes. Part VI. Formation of 4-nitrocyclohexa-2,5-dienones in the nitration of bromo-, acetoxy- and methoxy-arenes

Blackstock, D. J.; Hartshorn, Michael P.; Lewis, Alan J.; Richards, K.; Vaughan, J.; Wright, G. J.

doi:10.1039/j29710001212

Cited by 6 publications

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“…Striking examples arise from nitrations with solutions prepared from nitric acid and acetic anhydride, reagents for which there is still doubt about the identity of the electrophile.7 All involve intermediates of the type W;R, where R is methyl or some related hydrocarbon side chain. [8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23][24] Examples are the stereoisomers la and lb from o-xylene.8,9 The position which captures acetate can also be substituted, as in the adducts from p-xylene9,20 and 3,4-dimethylanisole.15 li JJi Other nucleophiles such as the nitrate ion can capture Wi's. 13 Acidolysis of nitroacetates of the kind mentioned regenerates the W; which can attack reactive aromatics; loss of nitrous acid then gives biaryls.17,21…”

Section: Consequences Of Ipso Attackmentioning

confidence: 99%

Ipso attack in aromatic nitration

Moodie¹,

Schofield²

1976

Acc. Chem. Res.

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Aromatic Nitration 287ate), the necessary internal return results in insignificant oxygen ~c r a m b l i n g .~~ If ion pairs formed under solvolytic conditions undergo rearrangement, attack by an added nucleophile, although rate limiting, must always suppress rearrangement20~38kv3Q since no example of skeletal rearrangement accompanying second-order substitution has ever been reported, even for the potentially favorable neopentyl case.75 These ion pairs must be "more intimate than intiand must thus behave like polarized RX molecules. This is what we believe they are, but we see no reason to call them ion pairs, for in such terms a methyl iodide molecule could be regarded as an ion pair by virtue of the C-I bond polarity.43 This would be fine in the present context since mechanistic distinction would be lost, but chemical problems cannot be solved by such semantic extensions, although we agree with the view that genuine ion pairs may possess a degree of covalent character. In fact, the postulation of ion-pair intermediates (and their formation with solvent assistance) in simple primary and secondary substrate solvolysis in reasonably nucleophilic solvents may be incorrect, and sN2 solvent attack may be the favored mode. We know of no evidence that demands intermediates in such simple solvolyses, and specifically intermediates formed without solvent or neighboring group assistance. If so, (74) A. F. Diaz, I. Lazdins, and S. Winstein, J. Am. Chern. Soc., 90, 1904 (1968). If such scrambling were detected it would still be difficult to prove that it did not occur in a mechanistic blind alley (see also ref 5). (75) Reference 1, p 742. See also G. M. Fraser and H. M. R. Hoffmann, Chem Cornrnun, 561 (1967). (76) Reference 7, p 366.there is no reason why they should intervene in nonsolvolytic substitutions with stronger nucleophiles.In summary, the "extra-intimate ion pair" is in our opinion a polarized RX molecule. The polarization arises from approach of N-, and the energy buildup needed to cross the sN2 potential barrier arises largely from solvent re~rganization~~ attendant on the merging of the original Nand RX solvation shells. We deliberately choose these words to mimic Bordwell's description of an ion-sandwich intermediate,26 noting that Bordwell himself has not been definite in postulating actual intermediacy. His results could equally well be rationalized in terms of a loose sN2 transition state (4) for his tertiary substrate and a tighter transition state (3) for the model primary system.In conclusion, the verdict which must be passed on Sneen's proposed universal unification of s N 1 and SN2 mechanisms is one which is unique to the Scottish legal system, and so I turn to the words of my forbears in stating "not proven". A more positive conclusion is not presently available, but we note that strides in this direction are being made through heavy atom isotope effect studies.45 I warmly thank Professors P. B. D. de la Mare, J. M. Harris, P. v. R. Schleyer, J. Seyden-Penne, R. A . Sneen, and J. Warkentin for ex...

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Section: Consequences Of Ipso Attackmentioning

confidence: 99%

Ipso attack in aromatic nitration

Moodie¹,

Schofield²

1976

Acc. Chem. Res.

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“…The latter was presumably formed by elimination of nitrous acid from the diene adduct. The diene adduct could not have eliminated nitrous acid before the sample for analysis was added to the sodium hydroxide since the product, 3,4-dimethylphenylacetate, reacts further with nitric acid to give a nitrodienone (14). Considerable heat was evolved when the sample (acetic anhydride solvent) was added to the sodium hydroxide solution and it is not surprising that decomposition of adduct to phenyl acetate and further hydrolysis of the latter to phenoxide was substantially quantitative.…”

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confidence: 99%