Organomagnesium Compounds

Organomagnesium Compounds

 

compounds that contain a carbon-magnesium bond. Two types of organomagnesium compounds are known: (1) complete compounds, such as magnesium dialkyls or magnesium diaryls, R2Mg; and (2) mixed compounds, such as alkyl magnesium or aryl magnesium halides, RMgX (X = Cl, Br, I). Complete organomagnesium compounds are crystalline substances and are highly sensitive to the effects of oxygen, moisture, and carbon dioxide (they are self-igniting). Such compounds were first produced in the mid-19th century using the reaction of organomercuric compounds, R2Hg, with magnesium; no use was found for them in organic synthesis.

In 1900 the French chemist F. Grignard developed a simple method of preparing mixed organomagnesium compounds and demonstrated a wide range of possible uses for them in organic synthesis. He established that metallic magnesium in absolute (anhydrous) ether reacts with alkyl or aryl halides, RX, to form compounds that pass into the ether solution. These compounds, known as Grignard reagents, are extremely unstable in free form. Therefore, they are not isolated but rather are used in the form of solutions, which are stable in the absence of moisture and atmospheric oxygen.

Subsequently, methods were developed for the preparation of Grignard reagents in hydrocarbon media (for example, benzene, xylene, and toluene) and in the absence of a solvent, which resulted in the possibility of using organomagnesium compounds in industry. However, the most widespread method has proved to be RMgX synthesis using ether solvents. An increase in the solvating properties of the solvent simplifies the formation of Grignard reagents. For example, vinyl halides, CH2 = CHX, do not react with magnesium in ether but rather form organomagnesium compounds in tetrahydrofuran (H. Normant). Ethynyl magnesium halides may be produced by the interaction of alkyl magnesium halides and acetylene derivatives (Ž. Jocic):

C6H5C≡CH + C2H5MgBr - C6H5C≡CMgBr + C2H6

Organomagnesium compounds are widely used in the preparation of various types of organic compounds. The industrial synthesis of certain organosilicon compounds, aromatic substances, and Pharmaceuticals is carried out with the aid of organomagnesium compounds.

REFERENCE

Ioffe, F. T., and A. N. Nesmeianov. “Magnii, berilii, kal’tsii, strontsii, barii.” In the collection Metody elementoorganicheskoi khimii [part 1]. Edited by A. N. Nesmeianov and K. A. Kocheshkov. Moscow, 1963.

B. L. DIATKIN

References in periodicals archive ?
In 1912, Grignard received the Nobel Prize in Chemistry for his outstanding research work on organomagnesium compounds.
After some initial frustration at being excluded from the honour, Philippe Barbier, who after all had started the study on organomagnesium compounds [11], bore no ill- will toward Grignard, and in fact the two remained on good terms.
In the tradition of the Patai Series The Chemistry of Organomagnesium Compounds treats all aspects of functional groups, containing chapters on the theoretical and computational foundations; on analytical and spectroscopic aspects with dedicated chapters on Mass Spectrometry, NMR, IR/UV, etc.