Grignard reagents from indole

The aforementioned mechanism is supported by the following experimental data. When oxime 13 was treated with Grignard reagent, 3% of the indole 15 was isolated, indicating the possible existence of nitrene intermediate 14. A 2-phenylazirine intermediate, on the other hand, has been isolated and characterized from the reaction under carefully controlled conditions (adding Grignard reagent to the oxime in toluene). ... 

Sanna reported that l,3-di(3-indolyl)-l,3-dioxo-%-propanc (266) and l,4-di(3-indolyl)-l,4-dioxo-M-butane (267) were formed by the action of malonyl chloride and succinyl chloride, respectively, on the indole Grignard reagent in ether, and analogous products could be obtained from 2-methylindole. 

A number of diindolylmethane derivatives including 336, 338, 339, 340, and 341 have been obtained by the action of the appropriate ketones, under fairly vigorous conditions, on the Grignard reagents derived from indole or 2-methylindole. ... 

Ingraffia studied the oxidation of the Grignard reagents derived from indole, skatole, and 2-methylindole with hydrogen peroxide and... 

The tenth volume of this serial publication comprises six chapters, four of which deal with the general chemistry of a specific group of heterocyclic compounds pyridopyrimidines (W. J. Irwin and D. G. VVibberley), benzofuroxans (A. J. Boulton and P. B. Ghosh), isoindoles (J. D. White and M. E. Mann), and pyrylium salts (A. T. Balaban, W. Schroth, and G. Fischer). The remaining chapters are concerned with indole Grignard reagents (R. A. Heacock and S. Kasparek) and with cyclic hydroxamic acids (J. B. Bapat, D. St. C. Black, and R. C. Brown).The international flavor of the publication is preserved our contributors come from six countries in three continents. 

B Add 30 g (II) over one-half hour to 420 ml methyl iodide and let stand fifteen hours at 5°. Separate the iodomethylate which precipitates, dry briefly at 50° and heat with vigorous stirring at 80° for two hours with 60 g NaCN in 1 L water. Extract with CHC13, dry and evaporate in vacuum the extract and dissolve the residue in 250 ml ether. Filter, evaporate in vacuum to a few ml and precipitate the acetonitrile (III) by adding petroleum ether. The acetonitrile can also be prepared directly from the indole via the Grignard reagent as given elsewhere here. 

To the Grignard reagent prepared from 2.4 g Mg, 10 ml anisole and 16 g ethyl iodide, add 7.8 g indole in 10 ml anisole. Stir and cool to 0°. Slowly add dropwise 5.5 g Cl-acetonitrile in 40 ml anisole. Warm to room temperature and stir heat to 60-70° on water bath (a reddish precipitate forms over about twenty minutes). Cool and purify and convert to the dialkyltryptamine as described earlier. Tryptamines JOC 24,894(1959)... 

Kondo employed the Kumada coupling using the Grignard reagents derived from 2- and 3-iodo-l-(phenylsulfonyl)indole to prepare the corresponding phenyl derivatives in 50% yield [92], Widdowson expanded the scope of the Kumada coupling and provided some insight into the mechanism [93],... 

Substituted indoles from the reaction of ort/jo-substituted nitroarenes and vinyl Grignard reagents. 

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