Abstract
Chloromagnesium bis(2,3,5,6-tetrachlorophenyl)copper, prepared from two equivalents of 2,3,5,6-tetrachlorophenylmagnesium chloride and one equivalent of copper(I) chloride inTHF, reacts with one equivalent of butyllithium at −78°C to give, subsequent to derivatisation with chlorotrimethylsilane and then with acetyl chloride, (1-acetyl-2,3,5,6-tetrachlorophenyl)trimethylsilane (20%), 1-(trimethylsilyl)-2,3,5,6-tetrachlorobenzene (17%) and 1-acetyl-2,3,5,6-tetrachlorobenzene (34%) along with some trace products. The formation of these products is explained on the basis of the intermediate formation of chloromagnesium bis(1-lithio-2,3,5,6-tetrachlorophenyl)copper, a functionalised cuprate reagent.
Zusammenfassung
Chlormagnesium-bis(2,3,5,6-tetrachlorphenyl)kupfer, das aus zwei Äquivalenten 2,3,5,6-tetrachlorphenylmagnesiumchlorid und einem Äquivalent Kupfer(I)chlorid inTHF hergestellt wurde, ergab mit einem Äquivalent Butyllithium bei — 78 °C nach Derivatisierung mit Chlortrimethylsilan und dann mit Acetylchlorid folgende Produkte: (1-Acetyl-2,3,5,6-tetrachlorphenyl)trimethylsilan (20%), 1-(Trimethylsilyl)-2,3,5,6-tetrachlorbenzol (17%) und 1-Acetyl-2,3,5,6-tetrachlorbenzol (34%) neben einigen weiteren Produkten in Spuren. Die Bildung der genannten Produkte wird mit Chlormagnesium-bis(1-lithio2,3,5,6-tetrachlorphenyl)kupfer, einem funktionalisierten Cuprat-Reagens, als intermediär gebildeter Verbindung erklärt.
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References
Gschwend H. W., Rodriquez H. R., Org. Reactn.26, 1 (1979);Gilman H., Morton jr., J. W., Org. Reactn.8, 258 (1954).
Jukes A. E., Adv. Organometal. Chem.12, 215 (1974);Posner G. H., Org. Reactn.19, 1 (1972);Normant J. F., Synthesis1972, 63;Posner G. H., Org. Reactn.22, 253 (1975).
Posner G. H., An Introduction to Synthesis Using Organocopper Reagents. New York: J. Wiley. 1980.
Normant J. F., Pure Appl. Chem.50, 709 (1978).
Tochterman W., Angew. Chem., Internat. Ed.5, 351 (1966);Wittig G., Quart. Rev.20, 191 (1966).
Keller R. N., Wycoff H. D., Inorg. Syn.2, 1 (1964).
Rahman M. T., J. Organometal. Chem.225, 25 (1982).
Gilman H., Schulze F., J. Amer. Chem. Soc.47, 2002 (1925).
Shiina K., Brennan T., Gilman H., J. Organometal. Chem.11, 471 (1968).
Tamborski C.,Soloski E. J.,Dills C. E., Chem. and Ind.1965, 2067.
Webb A. F.,Gilman H., unpublished studies.
Shiina K., Gilman H., J. Amer. Chem. Soc.88, 5367 (1966).
Gilman H., Swiss J., J. Amer. Chem. Soc.62, 1847 (1940).
Jukes A. E., Dua S. S., Gilman H., J. Organometal. Chem.21, 241 (1970).
Rahman M. T., Gilman H., J. Indian Chem. Soc.53, 582 (1976).
Smith jr. M. R., Rahman M. T., Gilman H., Organometal. Chem. Syn.1, 295 (1971).
Negishi E.-I., Organometallics in Organic Synthesis, Vol. I, part II. New York: J. Wiley. 1980.
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Rahman, M.T. The reaction of chloromagnesium bis(2,3,5,6-tetrachlorophenyl)copper with butyllithium. Monatsh Chem 114, 445–452 (1983). https://doi.org/10.1007/BF00798443
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DOI: https://doi.org/10.1007/BF00798443