4 Be ting to former RG foinenis poiehoe on the action of organomagnesium 
pounds on intracyclic oxides, it ought to be expected that on treatment of cineole 
h such bodies an additional compound should be formed. Grignard’), for instance, 
found that cineole, indeed, forms with methylmagnesium iodide an additional compound 
. af reacts extremely violently when heated ‘to 160°. C.F. van Duin?) recommends 
sion of 56 g. methylmagnesium iodide in ether and after several hours’ heating are 
-to stand for three or four days. The ether is then distilled off and the flask heated 
: to 160°; the reaction commences and proceeds without external application of 
_ hea . The reaction product is fractionated in vacuo and the distillate collected up to 
ES 50 (21 mm.). By shaking with resorcinol solution, the unattacked cineole is removed 
_ the result is a liquid of the b.p. 170 to 180° (¥59 mm.). consisting of a mixture 
‘hydrocarbons CioFlie,. from: which, however, crystalline derivatives’ could not be> 
Se oduced. Oxidation with MnO.K led to acetone and oxalic acid. When using ethyl- 
a. snesium bromide, the reaction proceeded less violent and resulted principally in - 
“unchanged cineole, in addition to a hydrocarbon CioHis. With phenylmagnesium 
b romide, the reaction proceeded differently; an addition product results also, but it — 
‘re nains unchanged below 200° and yields by further treatment cineole in addition to. 
_ Farthermore, the author has found that cineole Seces be reduced according. S ? 
‘Sa Z oS method. 
oo 
Priciisieipine. Some samples of ib duopine which were subinitiod to us for. 
camination. from different parts and originated — apparently from the same source, 
vee adulterated in a most extraordinary and extense manner. They consisted, namely, 
) one-half of sodium sulphate! Evidently, the adulterator did not command much skill, 
“ay ice sodium sulphate reveals its presence by its incombustibility as well as by its 
, ns solubility i in alcohol and ether. Heliotropine being used mostly i in alcoholic solution, 
the consumer will soon notice the sophistication: 
a When treating the sample with ether on_a filter, the Gulphate fernatnietl ieoluble: 
mounting to 50 to 52 per cent. After evaporating the solvent the residue of helio- 
c opine showed in all cases the correct m. p. of 35 to 36°, thus manifesting that the 
| terator had contented himself with this one POP SH ee Or: 
"According to the nature of the solvent cee the action of chlorine or bromine 
1 piperonal (heliotropine) passes off. in a different manner. A. M. Bleakly Orr, 
. Robinson and M. M. Williams®) found that. when preparing bromopiperonal » by 
| ening piperonal with bromine in acetic acid solution the yield was unsatisfactory, 
aldehyde group being partly substituted by bromine. In a neutral solvent, such - 
, carbon disulphide or carbon tetrachloride, the yield of bromo- or of 6-chloropiperonal 
Ee: "excellent, the formation of by-products — being reduced to a minimum; when 
7 malogenating, however, in acetic acid solution, 4, 5- dibromo- or 4, 5-dichlorocatechol 
om ett lylene ether result as Py paper ‘m. p. 86° and 820° respectively. 
TE 
4 a 
ms ws +) But delenit Ul. Soest: O44. — *) Kontakt S naa oan Wetetiseh:, ee Rana iess Wisk. en Natk. 
Affe - 2% (1917), 1366 ; Chem, Zentratbl. 1918, 1. 622.. — *) Journ. chem. Soc. 111 NE 946. 3 
the e following working method as being the best. 52 g. cineole are added to a sus- oa 
