THE MECHANISM OF THE REACTION BETWEEN KETENES AND THE GRIGNARD REAGENT.

Henry Gilman, L. C. Heckert

J. Am. Chem. Soc., 1920, 42 (5), pp 10101014 DOI: 10.1021/ja01450a015 Publication Date: May 1920

THE YIELDS OF SOME GRIGNARD REAGENTS

Henry Gilman, Roy McCracken J. Am. Chem. Soc., 1923, 45 (10), pp 24622466 DOI: 10.1021/ja01663a031 Publication Date: October 1923

THE QUANTITATIVE ESTIMATION OF THE GRIGNARD REAGENT1

H. Gilman, P. D. Wilkinson, W. P. Fishel, C. H. Meyers
J. Am. Chem. Soc., 1923, 45 (1), pp 150158 DOI: 10.1021/ja01654a022 Publication Date: January 1923

A QUALITATIVE COLOR TEST FOR THE GRIGNARD REAGENT

Henry Gilman, F. Schulze
J. Am. Chem. Soc., 1925, 47 (7), pp 20022005 DOI: 10.1021/ja01684a032 Publication Date: July 1925

A STUDY OF THE OPTIMUM CONDITION FOR THE PREPARATION OF ETHYLMAGNESIUM IODIDE

Henry Gilman, Charles H. Meyers
J. Am. Chem. Soc., 1923, 45 (1), pp 159165 DOI: 10.1021/ja01654a023 Publication Date: January 1923

SOME SIDE REACTIONS IN THE PREPARATION OF ALKYLMAGNESIUM HALIDES

Henry Gilman, Robert E. Fothergill
J. Am. Chem. Soc., 1928, 50 (12), pp 33343341 DOI: 10.1021/ja01399a027 Publication Date: December 1928

THE CONSTITUTION AND THE DISSOCIATION OF THE GRIGNARD REAGENT1

Henry Gilman, Robert E. Fothergill
J. Am. Chem. Soc., 1929, 51 (10), pp 31493157 DOI: 10.1021/ja01385a040 Publication Date: October 1929

IMPROVEMENTS IN THE METHOD FOR THE PREPARATION OF MERCURY DIALKYLS FROM ORGANOMAGNESIUM HALIDES
Henry Gilman, Robert E. Brown
J. Am. Chem. Soc., 1929, 51 (3), pp 928930 DOI: 10.1021/ja01378a042 Publication Date: March 1929

THE PREPARATION OF MERCURY DIALKYLS FROM ORGANOMAGNESIUM HALIDES

Henry Gilman, Robert E. Brown J. Am. Chem. Soc., 1930, 52 (8), pp 33143317 DOI: 10.1021/ja01371a045 Publication Date: August 1930

THE DISTILLATION OF GRIGNARD REAGENTS

Henry Gilman, Robert E. Brown J. Am. Chem. Soc., 1930, 52 (11), pp 44804483 DOI: 10.1021/ja01374a043 Publication Date: November 1930

THE EFFECT OF RAPID ADDITION OF HALIDE ON THE YIELDS OF SOME GRIGNARD REAGENTS
Henry Gilman, E. A. Zoellner, J. B. Dickey J. Am. Chem. Soc., 1929, 51 (5), pp 15831587 DOI: 10.1021/ja01380a043 Publication Date: May 1929

Reaction conditions
In reaction involving Grignard reagents, it is important to exclude water and air, which rapidly destroy the reagent by protonolysis or oxidation. Since most Grignard reactions are conducted in anhydrous diethyl ether or tetrahydrofuran, side-reactions with air are limited by the protective blanket provided by solvent vapors. Small-scale or quantitative preparations should be conducted under nitrogen or argon atmospheres, using air-free techniques. Although the reagents still need to be dry, ultrasound can allow Grignard reagents to form in wet solvents by activating the magnesium such that it consumes the water. [11] In the Grignard formation reaction, radicals may be converted into anions. See: H. J. R. de Boer, O. S. Akkerman, F. Bickelhaupt, Carbanions as intermediates in the synthesis of Grignard Reagents, Angew. Chem. Int. Ed. 27, 687 - 689, 1988. G. P. M. van Klink, H. J. R de Boer, G. Schat, O. S. Akkerman, F. Bickelhaupt, A. Spek, Carbanions as Intermediates in the Formation of Grignard Reagents, Organometallics 21, 2119 2135, 2002.

Gallery

Magnesium turnings placed on a flask.

Covered with THF and a small piece of iodine added

A solution of alkyl bromide was added while heating.

After completion of the addition, the mixture was heated for a while.

Formation of the Grignard reagent had completed. A small amount of magnesium still remained in the flask.

The Grignard reagent thus prepared was cooled to 0C before the addition of carbonyl compound. The solution became cloudy since the Grignard reagent precipitated out

A solution of carbonyl compound was added to the Grignard reagent

The solution was warmed to room temperature. The reaction was complete