— 139 — 



Alcohols. 



We have already previously referred to the glucosides of menthol 

 and borneol prepared by E. Fischer und K. Raske 1 ). Since then, E. Fischer 

 and B. Helferich 2 ) have described the glucosides of cetylalcohol, geraniol, 

 ci/cfohexanol, benzylalcohol and glycolic acid. /?-Geraniol-d-glucoside was 

 prepared by shaking up geraniol with aceto-bromoglucose in ether with 

 oxide of silver. When the excess of geraniol had been blown off with 

 steam, an oil remained behind from which, after prolonged standing, tetr- 

 acetyl-/?-geraniol-d-glucoside crystallised out. This body melts at 29 to 30°. 

 After saponification with barium hydroxide, the /2-geraniol-d-glucoside was 

 obtained from the acetylated compound. Dried over phosphorus pentoxide 

 this glucoside gave [<*] D27 o — 37,25°. It is tolerably hygroscopic, has an 

 exceedingly bitter taste, and melts at 58°. When the aqueous solution 

 is evaporated the geraniol glucoside is left behind in the form of beauti- 

 ful hydrated needles, Cie H 2S 6 -j- H 2 O. The glucoside dissolves very rea- 

 dily in alcohol and water, less readily in acetone and acetic ester, and is 

 very little soluble in ether and light petroleum. 



Tetracetyl-/?-benzyl-d-glucoside, which is prepared in a similar manner, 

 melts, not very definitely, between 96 and 101°; ^-benzyl-^-glucoside 

 melts at 123 to 125°. Tetracetyl-/2-q/dohexanol-d-glucoside occurs in long 

 needles with a silky lustre, m. p. 120 to 121°. /^-CfycZohexanoI-d-glucoside 

 melts between 133 and 137°. 



By condensing the hydrobromic ester of geraniol (or of linalool) 3 ) 

 with malonic ester or acetic ester, Dupont and Labaune 4 ) have prepared 

 certain new derivatives of geraniol or linalool, as the case may be. 



To the alcoholic solution of sodium malonic ester they added the 

 bromide by degrees, the temperature being meanwhile kept at about 10°, 

 as otherwise geranyl ethyl ether would have been formed. The principal 

 product obtained was a substituted malonic diethyl ester, answering to 

 formula I, which upon saponification yielded an acid (II) from which on 

 distillation in vacuo one molecule carbon dioxide was split off, with 

 formation of a substituted acetic acid (III) (b. p. 145 to 146° at 5 mm.; 

 b. p. of the ethyl ester 127 to 128° at 5 mm.). It was impossible to convert 

 the ester into a cyclic derivative by treating it with acids, even sulphuric 

 acid of 66° B was without effect in the cold. In the course of the reduction 

 of the ester of the substituted acetic acid with sodium and alcohol, an 

 alcohol (IV) was obtained which, when regenerated from the phthalic ester, 

 was found to possess the following constants: b. p. 119° (5 mm.), di 8 o 0,8956, 



r ) Berl. Berichte 42 (1909), 1465. Comp. Report October 1909, 78. 



2 ) Liebigs Annalen 383 (1911), 68. 



8 ) Comp. Report April 1910, 172; October 1910, 188. 



4 ) Berichte von Roure-Bertrand Fils, April 1911, 3. 



