ON THE APPLICATIONS OF GRIGNARD’S REACTION. 
product, whilst benzoic acid and benzophenone were also obtained. In 
fact the experimental conditions may be so adjusted! that no benzoic 
acid is obtained at all. The formation of triphenylcarbinol is represented 
as follows :— ; 
C,H, MgBr + CO, = C,H, . COOMgBr 
Coo 7 oMake 
C,H,. COOMg Br+ C,H,MgBr= C 
0,H,7 \NOMgBr 
C,H, 
C,H, ye Mgbr ae 
Ne + 0,H,MgBr = 0,H,YC. OMgBr + MgO + MgBr, 
C,H,7 NOMgBr 
C,H, 
CH, CH, 
cade . OMgBr + H,0 = cade OH + MgBromt 
C,H, C,H; 
Tertiary alcohols may also be obtained directly from carboxylic acids ? 
by the action of an excess of the Grignard reagent ; thus phenyldiethyl- 
carbinol, C;H,;(C,H;).C . OH, is formed from benzoic acid and magnesium 
ethyl bromide. Metallic salts of carboxylic acids may be applied in a 
similar manner,’ thus trimethylcarbinol is formed from potassium acetate 
and magnesium methy] iodide. 
The synthesis of tertiary amino-alcohols from esters of amino-acids 
has been studied more particularly by Paal.! For example, magnesium 
phenyl bromide and ethyl glycollate, NH,.CH,.COOC,H;, form 
diphenylhydroxyethylamine, NH, . CH, . C(COH)(C,H;).. 
After Houben® had shown that lactones when acted on by the 
Grignard reagent give tertiary alcohols, Paal and Hérnstein® prepared 
1 : 1-diphenyl-d-sorbitol, CH,OH . (CHOH),.C(OH)(C,H;)2, by acting 
on the acetyl derivative of d-gluconic lactone with magnesium phenyl 
bromide. 
A very convenient method for preparing ditertiary glycols was 
employed by Valeur,’ who acted on esters of dicarboxylic acids 
with an excess of the Grignard reagent; in this manner methyl 
oxalate and magnesium phenyl bromide yield benzpinacone, 
(C,H;),C(OH) . C(OH)(C,H;),. Ditertiary glycols may also be ob- 
tained either from esters of ketonic acids or from diketones; thus 
Grignard § obtained the glycol 
CH, . C(OM)(C,H,,). CH, . OH, . C(OH)(C,H,,), 
from magnesium isoamylbromide and ethyl levulate, 
OH, .CO.CH,. CH, . COOC,H,; 
whilst Zelinsky ® obtained the pinacone, (CH;), .C(OH) . C(OH)(CH3)., 
from diacetyl, CH,.CO.CO.CH:;, and magnesium methy! iodide. 
' Ber., 1907, 40, 1584. 
? Farbenfabriken vorm. F. Bayer and Co., D.It.-P., 1906, 166898. 
% Thid., 1906, 166899. 
‘ Ber., 1905, 38, 1686. Compare ibid., 1906, 39, 810, 2062, 4344. 
5 Thid., 1904, 37, 489. 
® Thid , 1906, 39, 1361, 2823, 2827. 
7 Compt. rend., 1903, 136, 694; Bull. Soc. Chim. 1903, 29, 683. Compare 
Dilthey and Last, Bez., 1904, 37, 2639. 
5 Compt. rend., 1902, 185, 627, ® Ber., 1902, 35, 2138. 
