326 



SCIENCE 



[N. S. Vol. XXVII. No. 687 



Mesoxalic Esters and their Reaction ivith 



Hydrazin: Eichard S. Curtiss and P. 



T. Tarnowski. 



Methylmesoxalate may be obtained by 

 saturating methylmalonate at 0° with 

 N2O3. After forty-eight hours it is dis- 

 tilled in vacuo. A yield of 80-85 per cent, 

 of (HO), > C = (COOCHg)^ can be crys- 

 tallized from the oily distillate. Hydrazin 

 hydrate and carbonate solutions react with 

 OC^(COOH), forming gummy and resin- 

 ous polymerization products. With care- 

 fully chosen conditions both the methyl 

 and ethyl esters give white crystalline 

 bodies. 



Owing to the ease of dissociation into 

 hydrazin and mesoxalic esters, the ques- 

 tion of an asymmetrical or a symmetrical 

 hydrazin derivative Avas not settled. PCI5 

 proves hydroxyl groi;ps present. Benzal- 

 delyl yields benzalazin and mesoxalic ester. 

 Benzoyl chloride gives symmetrical dibero- 

 zoyl hydrazin. Acids and alcoli solutions 

 dissociate these derivatives into hydrazin 

 and ester. 



Nitrosomalonic Esters: Richard S. Cur- 

 tiss. 



The action of N2O3 on malonic esters at 

 low temperatures forms a number of un- 

 stable nitrogen derivatives. From the 

 green oils thus obtained with ethyl mal- 

 onate two potassium salts have been ob- 

 tained: one (/3) canary yellow, the other 

 (a) nearly colorless. The molecular 

 weight and potassium determinations 

 show them to be salts of ethyl nitrosomal- 

 onate. The unstable nitroso ester formed 

 by dilute acids on the salt is pale green; 

 stains the cuticle like nitric acid ; gives ofP 

 nitrogen oxides in a desiccator, and is en- 

 tirely different in its properties from the 

 oxime of mesoxalic ester HON ^ C := 

 (Co2Co2H5)2. Saponification of the salt 

 with alcoholic potash yields a chrome 

 yellow potassium salt, which when treated 



with dilute H2SO4 and ether gives a yellow 

 oil not at all like the stable crystalline 

 oxime, HON= C = (COoH),. It is in 

 fact extremely unstable. "When air is 

 allowed to enter the desiccator, after its 

 ethereal solution has been freed of ethyl 

 in vacuo, it heats up, liberates gases and 

 puffs off white vapor, then flashes into 

 flame, and leaves the desiccator filled with 

 dense clouds of red oxides of nitrogen. 



The study of these compounds as well as 

 other nitrose and nitro derivatives of the 

 group 



is in progress. 



A Peculiar Decomposition of the Esters of 

 Formylchloridoxime : H. C. Biddle. 

 In the action of caustic potash on methyl 

 formylchloridoxime there are formed 

 methyl cyaniminocarbonic and diimino- 

 oxalie esters, nitrogen, and the potassium 

 salts of hydrocyanic, cyanic and oxalic 

 acids. 



The methyl fulminate naturally expected 

 is not obtained. If formed at all, the 

 fulminic ester probably condenses to the 

 double molecule, which then dissociates in 

 two directions, in one case giving rise to 

 oxalic acid and methyl alcohol and in the 

 other to cyanogen and alcohol, according 

 to the equation : 



SlCHjONC)^ + 4H,0 -» 



6CH3OH -I- H,C,0.i -f N2 -t- 2CjN,. 



The occurrence of cyaniminocarbonic 

 and diiminooxalie esters is readily ex- 

 plained by the tendency of cyanogen to 

 absorb alcohol in the presence of an alkali. 



The Constitution of Indigos and Related 

 Compounds: M. T. Bogert, K. G. Folk 

 and J. M. Nelson. 



Some recent work on indigos (chromo- 

 phore CO • C: C • CO) is discussed on the 

 hypothesis of the different colors being due 



