92 _ REPORT OF SCHIMMEL § Co. OCTOBER 1914/APRIL 1915. ; 
forms from the ester and passes by hydrolysis into phenylglyceric ester. This ester se 
transforms into the corresponding lactone and, by splitting off carbon dioxide, passes 
into phenylacetaldehyde. 
E. Spath*) describes an interesting synthesis of phenylacetaldehyde and of some . 
of its homologues. He found that the following reaction took place when alkyl-(aryl-) 
magnesium haloids acted on ethoxyacetal, which proved to be an easily accessible body: — 
(OC; Hs): CHe: CH(OC: Hs)2 + RMgX = C,H; OMgX + R-CH(OC, Hs): CH2(OC; H:;). 
In addition, vinyl ethers form according to the following transposition: — 
RCH(OC, Hs): CH2(OC: Hs) + RMgX = C.H;s0MgX -++ RH -+ RCH: CH(OC, Hs). 
When heated with dilute sulphuric acid, these ethers are saponified to aldehyde, 
passing through the stage of the unstable vinyl alcohol. 
In this way, the synthesis of aldehydes of the formula RCH.,:-CHO is given, and 
even most sensitive aldehydes may thus be prepared. 
The substituted phenylacetaldehydes are bodies of agreeable odour; they are 
highly sensitive towards acids and alkalis and congeal on long storage, foreman glassy 
substances. 
The phenylethylaldehyde, obtained by Spath through the action of riagteettlen phenyl 
bromide or iodide on ethoxyacetal and saponification of the resulting mixture, boiled 
between 84 and 86° (10 mm.) and showed all the properties of this body. 
From magnesium, o-iodotoluene and ethoxyacetal, o-methylphenylacetaldehyde was 
obtained, a colourless liquid of agreeable smell, boiling at 92° (10 mm.). m-Methyl- 
phenylacetaldehyde (b. p. 94° at 10 mm.) smells a little fainter than the o-combination. 
p-Methylphenylacetaldehyde boils at 96° (10 mm.). m-p-Dimethylphenylacetaldehyde 
boils between 112 and 114° (10 mm.), and o-p-dimethylphenylacetaldehyde, at from 
106 to 108° (10 mm.). o- and p-Methylphenylacetaldehydes were already known. 
Some years ago, F. W. Semmler and later on A. Wohl and R. Maag’?) have studied 
the action of acetic anhydride on phenylacetaldehyde. Further particulars on the 
subject are found in an article now published by E. Spath?), in which he reports, 
besides, regarding the action of acetic anhydride on isobutyraldehyde and cinnam- 
aldehyde. 
It is a well known fact that phenylacetaldehyde is much inclined to polymerize, 
and that it is difficult, in consequence, to preserve it unaltered. This phenomenon has 
been carefully studied by H. Stobbe and A. Lippold*). In order to purify the aldehyde, 
it was distilled from a flask, which permitted of determining. the temperature of the 
boiling liquid (on thermometer A), as well as that of the vapour passing over (on 
thermometer B)*). The main portion of the preparation passed over as almost pure 
phenylacetaldehyde. This is the period of distillation of the monomeric aldehyde. 
Thermometer A oscillated at first between 105 and 111° at 18 mm. and slowly rose on 
further heating from 112 to 160°, whereas thermometer B always showed 88° at 
18 mm. The distillate which passed over last was pure phenylacetaldehyde, which 
had formed by decomposition from the polymeric aldehydes present in the preparation. 
1) Monatsh. f. Chem. 36 (1915), 1. See also ibidem 85 (1914), 332. — 2) Berl. Berichte 42 (1909), 584; 
43 (1910), 3291; Report April 1909, 128. — *) Monatsh. f. Chem. 86 (1915), 29. — 4) Journ. f. prakt. Chem. 
HI. 90 (1914), 277. — 5) Stobbe and Reuss, Liebigs Annalen 891 (1912), 154. o 
