ON THE APPLICATIONS OF GRIGNARD S REACTION. 285 
however, a phenyl group is attached to the carbonyl group, a ketone is 
produced. Thus cinnamylidene acetophenone 
C,H, .CH : CH. CH: CH.CO.C,H; 
does not form, with magnesium phenyl bromide, the tertiary alcohol 
C,H, . CH : CH . CH : CH . C(OH)(C,H;)., but gives /3-phenyl /3-styry] 
propiophenone, C,H, . CH : CH . CH(C,H;) . CH, . CO . C,H;. 
Bauer ! obtains dialkylphthalides from phthalic anhydride ; thus with 
magnesium methyl-iodide 
co C(CH,) C(CH,), 
Téa 1H % Hd eS 
C,H, aoa Sree) “co > CH co pe 
a-Methy] phthalide 
CH(CH, 
ouZ ( 0 
~ CO 
is obtained from phthaldehydic acid.” 
Aldehydes. 
Aldehydes are obtained, according to Bouveafilt,? from disubstituted 
formamides :— 
Ht. CONRR’ +R’ MgX = HCR(OMgX) . NRR’ 
HCR'(OMeX) . NRR’+H,O=R”. CHO +NHRR’+ MgXOH 
Benzaldehyde, for example, was formed from ethyl formanilide and 
magnesium phenyl bromide. 
Bodroux‘ prepared a number of aldehydes in satisfactory yields from 
ethyl orthoformate ; benzaldehyde, for example, was obtained in a 90 per 
cent. yield :— 
CH(OC,H,), + C,H,;MgBr = MgBr(0C,H,) + C,H, . CH(OC,H,), 
C,H; . CH(OC,H;), + H,O + HCl=20,H,OH + HCl+ C,H, . CHO 
After Grignard had shown that secondary alcohols are formed from 
magnesium organic compounds (2 mols.) and formic esters (1 mol.), 
Gattermann and Maffezzoli® obtained aldehydes from magnesium organic 
compounds (1 mol.) and formic esters (3 mols.) ; secondary alcohols are 
formed at the same time, and the yields of aldehydes are not particularly 
good. The formation of o-toluyl aldehyde from o-bromotoluene is 
represented as follows :— 
CH, . C,H, . MgBr + H . COOC,H, = BrMg . 00,H, + CH, . C,H, . CHO 
Gattermann ® shows that ethoxymethyleneaniline may be used in 
place of ethyl formate ; anils are then formed from which aldehydes are 
obtained by the action of mineral acids, thus :— 
C,H, .N : CH . 0C,H,+RMgBr=0,H, . N : CHR+0,0,0MgBr 
C,H, .N : CHR+H,O=R . CHO+(,H, . NH, 
1 Ber., 1904, 87, 735 ; 1905, 38, 240. 
2 Simonis, Marben and Mermod, idid., 1905, 38, 3981. 
3 Compt. rend., 1903, 187, 987. 
4 Thid., 1904, 188, 92,700. Compare Tschitschibabin, Ber., 190t, 37, 186, 850. 
5 Ber., 1903, 36,4152. Compare Marbenfabriken vorm. F. Bayer and Co., D R.-P., 
1904, 157573. 
® Annalen, 1906, 847, 347. Compare Monier-Williams, 7rans, 1906, 89, 273. 
