Grignard Reagents

Haloalkanes and other compounds with the halogen atom bonded to either sp3-hybridized or sp2-
hybridized carbon atoms (aryl and vinyl halides) react with magnesium metal to yield organomagnesium
halides called Grignard reagents. Grignard reagents are usually prepared in diethyl ether
(CH3CH2O─CH2CH3). An ether solvent is essential for the reaction. The French chemist Victor Grignard
discovered this reaction in 1900, and it has been studied and used extensively ever since.

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Grignard reagents form easily from 1°, 2°, and 3° alkyl halides, although their reactivities differ. Aryl and
vinyl halides react somewhat more slowly, and the cyclic ether tetrahydrofuran (THF) is required to
prepare Grignard reagents of these compounds. The higher boiling point of the cyclic ether provides
more vigorous reaction conditions, but the rate of the reaction also increases because THF solvates the
Grignard reagent better than diethyl ether.

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Molecular model of a complex of methyl-magnesium chloride, a Grignard reagent, in which two

molecules of tetrahydrofuran, THF, are bound to magnesium. The model is based on the crystal
structure.

The order of reactivity of the halogens in haloalkanes is I > Br > CI > > F. Organofluorides are so
unreactive that they are never used to prepare Grignard reagents. Organohalogen compounds
containing bromine and chlorine are readily available, and are commonly used to prepare Grignard
reagents. Grignard reagents are used synthetically to form new carbon–carbon bonds. A Grignard
reagent has a very polar carbon–magnesium bond in which the carbon atom has a partial negative
charge and the metal a partial positive charge.

The polarity of the carbon–magnesium bond is opposite that of the carbon–halogen bond of
haloalkanes. Because the carbon atom in a Grignard reagent has a partial negative charge, it resembles a
carbanion, and it reacts with electrophilic centers such as the carbonyl carbon atom of aldehydes,
ketones, and esters. We will discuss this chemistry extensively in later chapters.

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Grignard reagents react rapidly with acidic hydrogen atoms in molecules such as alcohols and water.
When a Grignard reagent reacts with water, a proton replaces the halogen, and the product is an alkane.
The Grignard reagent therefore provides a pathway for converting a haloalkane to an alkane in two
steps.