Chemical and Physical Papers. 35 



ON THE REACTIONS OF THE FORMAMIDINES. 



Syntheses of Isoxazolon, Isoxazol, Cyanacetic and Benzoylacetic Acid De- 

 rivatives. 



By F. B. Dains and E. L. Griffin. 



IN previous papers it has been shown that compounds contain- 

 ing a methylene group, CH-.>, such as acetoacetic ester, ben- 

 zoyhicetio ester and cyanacetic ester, are capable of reacting with 

 substituted formaraidines yielding derivatives of the type XYC : 

 CHNHR, in which the two methylene hydrogens are replaced by 

 the grouping : CHNHR. Phenyl isoxazolon, another compound 

 containing methylene hydrogen, reacts in the same way, yielding 

 substituted aminomethylene derivatives of phenylisoxazolon. The 

 compounds made by this reaction were: 3-phenyl-4-anilidomethy- 

 lene - 5 - isoxazolon, 3 - pheny 1-4-o-toluidomethylene - 5- isoxazolon , 

 8-phenyl-4-p-toluidomethylene-5-isoxazolon, 3-phenyl-4-m-toluido- 

 methylene-5-isoxazolon, 3-phenyl-4-o-anisidomethylene-5-isoxazo- 

 lon, 3-phenyl-4-p-anisidomethylene-5-isoxazolon, 3-phenyl-4-p- 

 phenetidomethylene-5-isoxazolon, 3-phenyl 4-pseudocumidomethy- 

 lene•5-isoxazolon, 3-phenyl-4-nitroanilidomethylene-5-isoxazolon, 

 and 3 phenyl-4-p-bromanilidomethylene-5-i6oxazolon. 



It was found that derivatives analogous to these could be formed 

 by the reaction of either benzal-or anisal-methylisoxazolon on the 

 formamidines, the substituted aninomethylene derivatives of 

 raethylisoxazolon and benzal-or anisal-amines being obtained. 

 From benzalmethylisoxazolon were obtained 3-methyl-4-anilidome- 

 thylene-5-isoxazolon, 3 methyl-4-o-toluidomethylene-5-isoxazolon, 

 3-methyl-4-p-toluidomethylene-5-isoxazolon, 3-methyl-4-m-tolui- 

 domethylene-5-isoxazolon, 3-methyl-4-p-anisidomethylene-5-isoxa- 

 zolon, 3-methyl-4-o-ani8idomethylene-5-isoxazonon, 3-methyl-4-p- 

 phenetidomethylene-5-isoxazolon, and 8-methyl-4-m-xylidomethy- 

 lene-5-isoxazolon. From anisal methylisoxazolon and formami- 

 dines were made 3- methyl-4-anilidomethyiene - 5 -isoxazolon, 

 3-methyl-4-p-anisidomethylene-5-i8oxazolon, and 3-methyl-4-p8eu- 

 documidomethylene-o-isoxazolon. Anilidomethylememethylisoxa- 

 zolon and aniiidomethylene phenyl-isoxazolon were found to react 

 with bromine, with the loss of hydrobromic acid, forming mono- 

 brom derivatives, which on solution in alcohol go over to p-brom- 

 anilido-methylene-methyl-isoxazolon and p-bromoanilido methy- 



