Fbbbuaey 25, 1910] 



SCIENCE 



315 



but from the nature of the case, the degree of 

 accuracy attained by different investigators is 

 very variable. In the case of compounds followed 

 by (?) the classification is open to doubt. 

 Hyd/razones of Certain Oxy-Ketones ; Alkali-In- 

 soluble Phenols: Henkt A. Tokrey. 

 Although it is a very general rule that phenols 

 are soluble in aqueous alkalies there are certain 

 substances of this class that are marked excep- 

 tions. The phenolhydrazones of certain aceto- 

 phenols and acetonaphthols are entirely insol- 

 uble in aqueous alkalies. This alkali-insolubility 

 is determined by two conditions: (1) the free 

 hydroxyl group is ortho to the substituted ketone 

 side chain; (2) other substituting groups, as 

 OCH3, or hydrocarbon groups are present. 



The importance of the second condition is seen 

 in the fact that while the phenylhydrazone of 

 o-osyacetophenone is soluble in aqueous alkalies, 

 the same derivatives of paeonal or a-acetonaph- 

 thol are insoluble. The azines of a-acetonaphthol 

 is insoluble in aqueous alkalies, whereas in gen- 

 eral the azines have been found soluble, even 

 though the phenylhydrazones are insoluble. No 

 condensation between the imino and hydroxyl 

 groups has taken place. There seems to be no 

 evidence to suggest that these alkali-insoluble 

 phenols should be weaker acids than corresponding 

 bodies that are soluble. The acetyl derivatives 

 obtained by Auselmino from similar alkali-insol- 

 uble phenylhydrazones of oxyphenylaldehydes 

 point to the presence of the hydroxyl group. It 

 is possible that the consideration of a quinoid 

 structure may assist in the explanation of the 

 alkali-insolubility of these compounds. They 

 furnish an interesting instance of the effect that 

 a substituting group may have upon the whole 

 equilibrium of the molecule. 



Furoylacetic Ester and Furyl-Pyrazolones : Henet 



A. ToEBEY and J. E. Zanetti. 



Furoylacetic ester, as might be expected, closely 

 resembles acetaeetie ester and benzoylacetic ester. 

 Its oxime, however, is more stable, although it 

 can be converted into the corresponding isoxa- 

 zolone without difficulty. The comparative sta- 

 bility of the oxime shows that the furyl group 

 has a greater attraction for the hydroxyl of the 

 oxime radicle than would be indicated by the 

 position assigned to it by Hantzsch in his list of 

 groups arranged in order of their power of attrac- 

 tion for hydroxyl in this class of compounds. 

 Since pyromucic acid has a considerably higher 

 dissociation constant than either benzoic acid or 



acetic acid, the comparative stability of the oxime 

 of furoylacetic ester is better explained by the 

 views of Abegg, according to which the difference 

 in electrical charges of the groups influencing the 

 hydroxyl of the isonitroso group is considered. 



Furoylacetic ester forms hydrazolones easily 

 with hydrazines, thus with aryl hydrazines, 

 1-aryl 3-furyl 5-pyrazolones are given. As would 

 be expected, these pyrazolones show tautomeric 

 relationships. With benzaldehyde a condensation 

 product was formed with one molecule of the 

 pyrazolone and with diazo salts highly colored 

 azo compounds were prepared. Acetyl and benzoyl 

 derivatives were readily formed. 



From 1-phenyl 3-furyl-5-pyrazolon9 by the ac- 

 tion of methyl iodide the hydriodide of 1-phenyl 

 2-methyl 3-furyl-5-pyrazolone was obtained, an 

 analogue of the drug " antipyrine." Other salts, 

 such as the hydrochloride and hydrobromide, were 

 made, but owing to the negative nature of the 

 furyl group they are easily hydrolyzed by water 

 giving the free body in the form of an oil diffi- 

 cultly soluble in water. 



Methyl Phenyliminomalonate and its Reactions: 

 RiCHAED Sydney Cuetiss and F. Grace C. 

 Spencee. 



This compound C„HbN = CICOaCHa)^ is made 

 by the action of P2O5 on methyl anilinotartronate, 

 the addition product of aniline on methyl 0x0- 

 malonate. It shows remarkable reactivity at the 

 nitrogen-carbon double bond. Moisture of the air 

 rapidly changes it to methyl dianilinomalonate 

 and methyl dihydroxymalonate ; a complex reac- 

 tion, involving the formation of aniline and 

 methyl dehydroxy malonate and their interaction 

 to produce the final products. Aniline acts on 

 methyl phenyliminomalonate giving methyl dian- 

 ilinomalonate. Alcohols, amines and many other 

 classes of compounds containing easily dissociable 

 hydrogen, add directly to the double bonds. The 

 substance is a striking analogue of phenylisocy- 

 anate. Mercuric oxide oxidizes methyl anilino- 

 malonate yielding methyl dianilinomalonate and 

 methyl oxomalonate. This reaction is complex 

 and its mechanism may be explained by assuming 

 that methyl anilinotartronate first formed disso- 

 ciated to methyl phenyl iminomalonate, and that 

 this was changed by water into the final products 

 as stated above. Further studies are in progress 

 on phenyliminomalonates. 



On 4- and 5-acetamino Acetanthranils and Quin- 

 azoUnes derived therefrom: M. T. Boqert and 

 C. G. Amend. 



