— 188 — 



The chlorides which have been obtained by Dupont and Labaune 1 ) 

 by acting with hydrochloric acid gas upon linalool, have been more 

 closely investigated by the authors' 2 ). It appeared that the product 

 previously described as linalyl chloride was not quite uniform, but 

 probably also contained geraniol derivatives. For the preparation of 

 this chloride the authors have discovered a more suitable method, con- 

 sisting in introducing dry, powdered carbonate of potassium, suspended 

 in benzene, into a dry solution of geraniol in benzene and gradually dilut- 

 ing the mixture with a solution of one part trichloride of phosphorus to 

 two parts of anhydrous benzene. By this method 150 g geraniol yielded 

 100 to 110 g. hydrogen chloride esters of the same properties as those 

 described in the previous paper. 1-Linalool yielded the same product, but 

 from d-linalool the corresponding derivative was unobtainable, by-products 

 being formed which could not be altogether removed. 



The yield of esters of hydrogen bromide is greater than that of esters 

 of hydrogen chloride. Hydrobromic acid was allowed to act upon the 

 geraniol in the same manner as previously described for hydrochloric acid. 

 d-Linalool is readily esterifiable with hydrobromic acid, but not with hydro- 

 chloric acid. Geraniol, d-linalool and 1 -linalool all yield the same in- 

 ester: b. p. 102 to 103° (6 mm.), di 5 o 1,1450, n D15Q 1,507. When the 

 ester of hydrogen chloride prepared from geraniol is heated with melted 

 sodium acetate in the presence of toluene, a product is formed which 

 boils at 105 to 106° and possesses the properties of linalyl acetate. When 

 saponified, this substance yields an alcohol with the constants of linalool. 

 The action of sodium ethylate upon three samples of the ester of hydrogen 

 bromide prepared from geraniol, d-linalool and 1-linalool respectively gave 

 rise to a product boiling at 218°, with the constitution of an ether C12H22O. 

 Synthetic geranyl ethyl ether prepared by the authors also boiled at 218°. 

 Linalool ethyl ether (b. p. 192°), was obtained by them from ethyl bromide 

 and linalool-sodium (prepared with sodium amide). The ether obtained 

 from the hydrobromides which is referred to above is also, without doubt, 

 geranyl ethyl ether. 



When the hydrobromides derived from geraniol are allowed to stand 

 with oxide of silver at room-temperature, the result is a body boiling at 

 199 to 200°, and possessing the properties of linalool. This body is pro- 

 bably contaminated with small quantities of unsaponified bromide. 



The action of nitrate of silver in alcoholic solution upon the hydro- 

 chlorides does not (as was stated to be the case in Dupont and Labaune's 

 previous paper), result exclusively in pure linalool, but in 1-linalool, pro- 

 bably contaminated with geranyl ethyl ether, and possibly also with linalyl 

 ethyl ether. 



*) Berichte von Roure-Bertrand Fils October 1909, 21; Report April 1910, 172. 

 2 ) Berichte von Roure-Bertrand Fils April 1910, 42. 



