ON THE APPLICATIONS OF GRIGNARD’S REACTION, 989 
ether ; the compound of quinoline and magnesium phenyl bromide is 
represented as C,H,N . (MgBr)C,H,. j 
Forster and Judd,' in studying the action of magnesium methy] iodide 
on a-cyanocamphor, found that about 80 per cent. of the latter compound 
escaped attack by the reagent, whilst the remainder was converted into 
the imine 
CH. C(CH,) : NH 
EV gti 
| 
Nco 
which on hydrolysis gave acetylcamphor, 
When normal ethyl carbonate is added to the magnesium compound 
of a primary aromatic amine, one obtains a monosubstituted urethane,” 
thus ;— 
2C,H,NHMel + C0(00,H,), =(C,H, . NH),C(0C,H,) . OMgI + MgI(0C,H,) 
(C,H, . NH),C(OC,H,) . OMgI + H,O = C,H,NH, +C,H,NH . COOC,H, 
The application of the Grignard reagent for the preparation of 
diazoamino-compounds has been the subject of a series of papers by 
Dimroth.2 These compounds are obtained from diazobenzeneimide 
according to the scheme 
N 
C,H: Nn | + RMgX = 0,0,.N (MeX).N: NR 
N 
C,H, .N(MgX).N: NR + H,O = C,H,.NH.N:NR + MgXOH 
The method is particularly useful for the preparation of aliphatic or 
mixed aliphatic-aromatic diazoamino-compounds, for the preparation of 
which the older method of Griess is not available. Thus phenylmethyl- 
triazene, CH,.N,H. C,H, benzylmethyltriazene, CH, . N,;H.CH,C,H,, 
&e., have been prepared. Diazoaminomethane, CH;.N:N.NH.CHsz, 
was prepared from methyilazide, CH, NZ || , and magnesium methyl 
prep y Ne 8 y 
iodide, according to the scheme given above. The isolation of this in- 
teresting compound was accompanied with great difficulties, due, on the 
one hand, to its instability, and, on the other, to the ease with which it 
dissolves in all solvents tried. 
Alkyl and Aryl Metallic Compounds. 
Pfeiffer and Schnurmann‘ describe a method of preparing alkyl and 
aryl metallic compounds by interaction of metallic halides and the 
Grignard reagent either at the ordinary temperature or at 100°. Tin 
tetraethy], for example, is prepared from tin tetrabromide and magnesium 
ethyl bromide ;— 
SnBr, + 40,H,MgBr = Sn(C,H,), + 4MgBr, 
Other tin compounds, such as tin tetraphenyl, tin tribenzyl chloride, tin 
trimethyl iodide, &c., are also obtained by this method, which has also 
! Trans. Chem. Soc., 1905, 87, 368, 
* Bodroux, Compt. rend., 1905, 140, 1108. 
8 Ber., 1903, 36, 909; 1905, 38, 670; 1906, 89, 3905, 
: 4 Thid., 1904, 87, 319, 1125, 4617, 4618, &c. 
1907. u 
