ON THE APPLICATIONS OF GRIGNARD’S REACTION. 279 
general one. Thiophenols and selenophenols are formed in an analogous 
manner.! 
The action on p-quinones has been investigated by Bamberger and 
Blangey,? who obtain quinols, but in small yield. Werner and Grob* 
find that phenanthrene quinone and magnesium phenyl bromide give 
9 : 10-dihydroxydiphenyldihydrophenanthrene :— 
OH 
C,H, CO CH. CC 
C,H, 
PTS 
C,H,.CO CH. CC 
C,H 
Hydrocarbons. 
(a) Unsaturated hydrocarbons.—When the Grignard reaction is applied 
to aldehydes, ketones, &c., sometimes an unsaturated hydrocarbon is 
obtained instead of an alcohol. It is in fact often possible to select the 
experimental conditions so that either an alcohol or the unsaturated 
hydrocarbon, obtained from it by the elimination of water, is the product 
of the action ; for example, Grignard! obtains phenyldimethylearbinol, 
C,H, .C(OH)(CH;),, from magnesium methyl iodide (1 mol.) and aceto- 
phenone (1 mol.). If, however, magnesium methyl iodide (2 mol.) is added 
to acetophenone (1 mol.) the ether expelled and the residue heated for 
six hours at 100°, the unsaturated hydrocarbon, metho-(1’)-vinylbenzene, 
C,H 
(SG OH, 
CH,” 
results.° Similarly, it is possible to prepare from mesityl oxide 
CH 
Ye CH.CO.CH, 
CH, 
either the hydrocarbon 
CH CH 
"Nc: of 8 
CHA XS 
or the alcohol 
CHa 
De 1 CH. C(OH)(CHy),.’ 
CH, 
To quote a third example, Kay and Perkin,® starting with optically active 
ethyl A’-tetrahydro-p-toluate 
CH,.CH 
CH). cH ; Se .C00C,H, 
CH,. CH; 
2° 
' Wuyts and Cosyns, Bull. Soc. Chim., 1903 [8], 29, 689; Taboury, Buil. Soe, Chim., 
1904 [3], 31, 1183. 
2 Ber., 1903, 36, 1625. 3 Tbid., 1904, 37, 2892. 
* Compt. rend., 1900, 180, 1322. Compare W. H. Perkin, jun., and Pickles, Trans. 
Chem. Soc., 1905, 87, 671. 5 Klages, Ber., 1902, 35, 2633. 
® Grignard, Compt. rend., 1900, 180, 1324. 
7 Fellenberg, Ber., 1904, 37, 3678. 
8 Trans. Chem. Soe., 1906, 89, 839. Compare also ibid., 1905, 87, 1100. 
