636 REPORT— 1903. 



Preparation of Phenolbromoylueoside (C(;HjO.(OH)3 Br.O.Cy Hj). 



A solution of potassium phenolate in absolute alcoliol was allowed to act on a 

 solution of acetodibromoglucose in chloroform for fourteen days. The solution 

 was filtered, and the residue obtained on spontaneous evaporation was neutralised 

 with acetic acid and extracted with ether. When the ether was evaporated a 

 residue was obtained which, when recrystallised from dilute alcohol, gave beauti- 

 ful white needle-shaped crystals of phenolbromoglucoside, melting at 165° C. 

 The glucoside reduces Fehling's solution. It is easily soluble in ether, acetone, 

 and ethyl acetate, soluble in alcohol, and somewhat soluble in chloroform. It is 

 easily soluble in concentrated sodium hydroxide, and the solution, when carefully 

 neutralised, gives a precipitate which melts at 170°-1S0° C, and which reduces 

 Fehling's solution only after being hydrolysed by boiling with dilute acids. 

 The bromine in phenolbromoglucoside is not precipitated by silver nitrate solution. 



It ia hoped to replace the bromine atom in this compound by an amido-group, 

 and then by splitting off the phenol rest to obtain an amidoglucose, and thus 

 determine the position of the second bromine atom in acetodibromoglucose. 



5. Pre^yaration of Oximido-compounds. By W. Sloan Mills, M.A. 



As it seemed desirable that the work described in the paper on ' The Action of 

 Oxides of Nitrogen on Oximido-compounds ' should be extended to other oximido 

 compounds, j«-nitrobenzalisonitrosoacetone and cuminalisonitrosoacetone and some 

 of their derivatives were prepared. 



Molecular proportions of isonitrosoacetone and m-nitrobenzaldehyde were con- 

 densed to wi-iiitrobenzalisouitrosoacetone (C,;Hj-NO,,-CH = CH-CO-CH:NOH) by 

 means of sodium hydroxide. A theoretical yield was obtained. When recrystal- 

 lised from absolute alcohol it gave slightly yellow coloured crystals, melting at 

 164° C, which were easily soluble in acetone, ether and glacial acetic acid. It was 

 soluble in dilute sodium hydroxide. When treated with phenylhydrazine a 

 yellow crystalline hydrazone was formed melting at 99°-100° C. When heated 

 on a water-bath with excess of phenylhydrazine a dark-red insoluble precipitate was 

 obtained, which melted at 206°-207° C, and proved to be the dihydrazone of m-nitro- 

 benzalmethylglyoxal {C,H,(NO.,)GH = CH-C(:N-NHCsH,)-CH(NNll-0«H5)}. 



OT-Nitrobenzalisonitrosoacetoxime (CeH,(NO,)-CFI = CH-C = NOH-OH = NOH) 

 was isolated when the ketone was treated with free hydroxylamine. It is soluble 

 in glacial acetic acid, insoluble in absolute alcohol, and melts at 220° C. By the 

 action of semicarbazide on the ketone m - nitrobenzalisonitrosoacetone semi- 

 carbazone {C,H,(NO„)-CH = CH'C( = N-NirCO-NH„)'CH = NOH} was obtained 

 which melted at 196°-197° C. 



Cuminalisonitrosoacetone | (CH3)2CHC,,H^-CH = CH-CO-OH = NOH)} was 

 prepared by the condensation of cuminol and isonitrosoacetone. It was recrystal- 

 lised from benzene, giving beautiful sulphur yellow rectangular plates melting at 

 162°-163° C. It does not give readily a crystalline hydrazone. It is easily 

 soluble in ether and acetone, soluble in benzene, and insoluble in petroleum ether. 

 By the action of semicarbazide cuminalisonitrosoacetone semicarbazone 

 {(CH3),CH-C,H,CH = CHC(N-NH-C0-NH,)-CH = N0H} was obtained, which 

 melted at 176° 0. when recrystallised from dilute alcohol. It is easily soluble in 

 acetone and solvible in ethyl acetate and ether. When the ketone was treated 

 with free hydroxylamine in methyl-alcohol solution a beautiful white crystalline 

 oxime |(CH3),,CH-C,IVCH = CH-C = NOH-CH = NOH} was precipitated on the 

 addition of a little water. It melted at 192° C, and was easily soluble in ether 

 acetone and ethyl acetate, soluble in alcohol and benzene, and somewhat soluble in 

 chloroform. 



