ON THE APPLICATIONS OF GRIGNARD’S REACTION, 287 
is described. The method gives excellent yields, and appears to be 
particularly suitable for the preparation of esters from unstable tertiary 
alcohols. 
Nitrogen Compounds. 
Tn continuation of his work on the formation of ketones from nitriles, 
Blaise! describes the preparation of anilides from phenyl isocyanate, 
thus :— 
C,H, .N:C:0+BMgI=C,H,.N:Cé 
pou 
=> 0,H,.N:C -> O,H,NH . COR 
Nr 
Another method of obtaining anilides is given by Bodroux,’ who uses 
the magnesium organic compounds of primary aromatic amines. This 
type, RNHM¢gI, is obtained either by adding the amine to a cold ethereal 
solution of magnesium methyl iodide, or by the action of equimolecular 
amounts of methyl iodide and amine on magnesium in the presence of 
ether. When an ester of a monobasic acid is then added, and the product 
decomposed as usual by dilute acid, an almost theoretical yield of anilide 
-is obtained :— 
2RNHMg1 +B! . COOR!'=MgIOR’ +R’. C(NHR), . OMgI 
R’. C(NHR), . OMgl+HC1=R. NA, + MgICl+ BV .CO.NHR 
The action of magnesium organic compounds on mustard oils is 
analogous to the action on isocyanates. Sachs and Loevy * obtained a 
number of thioanilides according to the scheme 
RN i628 -R/Mel=R.Ns CCB!) S: Mel 
R.N:C(R’).S. Mgl+HCl=R. NH. CSR’+ MgCll 
Nitrosohydroxylamines are formed by the action of nitric oxide on 
the Grignard reagent, nitrosophenylhydroxylamine being formed, for 
example, in good yield from magnesium phenyl bromide :— * 
OMgBr 
NO O:N.N:0>0:N.NC  — O:N.NC 
\o,Hs No,H, 
Since carbon dioxide and sulphur dioxide form carboxylic and sulphinic 
acids respectively with a Grignard reagent, Wieland ° tried the action of 
nitrogen peroxide in the expectation of obtaining acids of the type 
R.NOOH. Instead of this type, however, he obtained, in the aliphatic 
series, /3/3-dialkylated hydroxylamines, R,N . OH, the nitrogen peroxide 
undergoing reduction. The preparation of 33-diethylhydroxylamine is 
described. Negative results were obtained in the aromatic series.” 
The action of magnesium phenyl bromide on /:-phenylhydroxylamine 
has been investigated by Busch and Hobein,’ who obtain a 20 per cent. 
1 Compt. rend., 1901, 132, 38, 478, 978. 
2 Thid., 1904, 138, 1427. 
3 Ber., 1903, 36,585; 1904, 37, 874. 
* Sand and Singer, ibid., 1902, 35, 3186; Annalen, 1903, 323, 190. 
5 Ber., 1903, 36, 2315. 
® Wieland and Gambarjan, idid., 1906, 39, 1499. 
? Thid., 1907, 40, 2099, 
