ON THE APPLICATIONS OF GRIGNARD’S REACTION. 278 
Lhe Applications of Grignard’s Reaction. 
By ALEX. McKenzir, M.A., D.Se., Ph.D. 
[Ordered by the General Committee to be printed in eatenso. | 
Introductory. 
In 1900 Victor Grignard! found that a vigorous action ensues whér 
magnesium powder is added to a mixture of methyl iodide and anhydrous 
ether. The magnesium gradually dissolves with the formation of a clear 
solution from which, on evaporation of the ether, a crystalline grey 
hygroscopic solid is obtained. If an aldehyde (1 mol.) is added to the 
ethereal solution obtained from magnesium (1 mol.) and methyl iodide 
(1 mol.), a vigorous action again takes place with the formation of a mag- 
nesium organic compound, which, when decomposed by dilute acid, gives 
a good yield of the corresponding secondary alcohol. 
Grignard found it possible by this method to obtain from benzalde- 
hyde, for example, a satisfactory yield of phenylmethylcarbinol” and the 
action is represented in the following manner :— 
CH,I + Mg=CH,MgI 
CH,MgI+C,H, . CHO=0,H,. CH(OMgI) .CH, 
C,H, .CH(OMgl) . CH, + H,O =C,H,. CH(OH). CH, + MgIOH 
Ketones, in an analogous manner, are readily converted into tertiary 
alcohols ; thus Grignard obtained phenyldimethylearbinol from aceto- 
phenone :— 
CH,I + Mg=CH,Mgl 
CH,MgI+CH,. CO. C,H, =(CH,),C(OMgl) . C,H, 
(CH,),C(OMgl) . C,H; + H.O =(CH,),C(OH). C,H; + MgIOH 
In his first paper Grignard also points out that other alkyl halides 
may be substituted for methyl iodide with equally satisfactory results. 
The successful application of the new reagent for the synthesis of 
alcohols from esters of aliphatic monobasic acids was described in the fol- 
lowing year.’ Formic esters are converted into secondary alcohols ; for 
example, diethylearbinol is obtained in a 73 per cent. yield from mag- 
nesium ethyl bromide and ethyl formate :— 
C,H,Br + Mg=C,H,MgBr 
OMgBr 
C,H,MgBr+H,C00C.H,=H. oteat, ; 
0C.H, 
OMgBr OMgBr 
00,1, 
H.CCO,H, +0,H,MgBr=H.CCC.H, +Me® 
Nour 
OC, H, CH, 
OMgBr OH 
IL. of err, +H,0=H, otoar, + MgBroH 
C,H, OH, 
1 Compt. rend., 1900, 180, 1522. 
2 Annales de UV Université de Lyon, 1901, &, 1. 
3 Compt. rend., 1901, 182, 336. 
1907. is 
