584 REPORT— 1902. 



silver oxide to a solution of the tri-methylic ether in a lavge excess of methyl 

 iodide, and boiling the mixture for several hours. After filtering and evaporating, 

 the product was distilled in vacuum, and tetra-methylic methyl glucoside obtained 

 as a colourless fairly mobile liquid, boiling at 144°-145° under 17 mm. pressure. 

 In different preparations the boiling-point was the same, and satisfactory results 

 were obtained in the combustions and Zeisel determinations. The specific rotation 

 at 20° of the pure substance proved to be + 127'88°, whilst a 5 per cent, solution in 

 alcohol gave (a)i/<^°= + 12778°. 



Hydrolysis of the Compounds. 



Both tri-methylic and tetra-methylic metb^'l glucoside when hydrolised give 

 compounds capable of reducing Fehling'.s solution, and thei'efoie ]irobably contain- 

 ing an ' aldose ' structure. On hydrolysis of the tri-methylic ether by means of 

 20 per cent. HCl, a colourless gum was isolated from the reaction products, which, 

 after drying at 110°, gave figures on combustion approximating to those required 

 for tri-methyl glucose. The substance reduced both Fehling's solution and an 

 ammoniacal solution of silver nitrate, and a qualitative Zeisel experiment showed 

 that the methoxyl groups had survived the hydrolysis. So far this body lias not 

 been obtained in a state of purity, but we are at present engaged in the preparation 

 of the compound on a larger scale, with a view to examining its properties and 

 investigating the special reactions of which it is capable. We likewise hope to 

 publish shortly an account of the alkylated glucose obtainable from the tetra- 

 methylic methyl glucoside, and to continue our experiments on other alkylated 

 sugars which are already partly prepared and examined. 



Alkylation of Acetone-vhmnnoside. 



According to Fischers formula for acetone-rhamnoside, the compound con- 

 tains two hydroxyl groups, and we find that the silver-oxide reaction can be 

 successfully carried out on the substance with the formation of di-methylic acetone- 

 rhamnoside. 



The rhamnoside, when dissolved in acetone, reacted energetically with silver 

 oxide and methyl iodide, and after filtration and evaporation the product was 

 distilled in vacuum. Complete alkylation was, however, only obtained by dis- 

 .solving the distilled product in methyl iodide and repeating the treatment with 

 silver oxide. On distillation, a coloiu-less pleasant-smelling oil was obtained 

 (boiling-point =115°-118° under 11 mm. pressure), which the combustion and 

 Zeisel results showed to be di-methylic acetone-rhamnoside. 



The compound is soluble in the ordinary organic solvents, and has scarcely any 

 action on Fehling's solution until hydrolised with IICl. 



A 5 per cent, solution in acetone had a specific rotation of — 24:"64° at 20°, this 

 result being in sharp contrast to the value of (a)i, for the parent substance, which 

 equals + 17-4°. 



Presumably the compound on hydrolysis splits oft" a molecule of acetone and 

 gives a di-methylic rhamnose, just as the rhamnoside itself yields acetone and 

 rhamnose. We are at present engaged in the investigation of this reaction, and it 

 is our intention to examine the hydrolysis product in detail, with a view to 

 establishing its reactions and constitution. 



5. Re^mrt on the Collections of Statintirs concerniny lite Training of 

 Chemists emj)Ioyed in English Chemical Industries. — See Iieports, 

 p. 97. 



0. Report on Isomeric Naphthalene Derivatives. — See Reports, p. 17G. 



7. Repiort on Isomorjjhons Sulphonic Derivatives of Benzene, 

 See Reports, p. ]80, 



