114 The Philippine Journal of Science i9i4 



Thiophthaloxime was prepared by adding 10 grams of 

 powdered phosphorous pentasulphide to 10 grams of phthaloxime 

 dissolved in 250 cubic centimeters of boiling xylol. The solution 

 upon continued boiling with a reflux condenser turns deep red 

 and deposits purple- to black-colored decomposition products. 

 After from two to three hours of gentle ebullition, the solution 

 is cooled and decanted from unchanged oxime, sulphides, and 

 decomposition products. The mother liquor deposits thio- 

 phthaloxime upon standing for some time in a cool place. The 

 yield is meager, seldom exceeding 10 per cent and frequently 

 even less. Larger amounts of original material give a lower per- 

 centage yield than when the reaction is carried out on a small 

 scale. 



The crude thio-oxime may be largely freed from phthaloxime 

 by recrystallization from benzol in which it is much more 

 soluble. Recrystallized from benzol and from alcohol, thio- 

 phthaloxime forms long red needles melting with decomposition 

 at 148°. 5 (corrected). The compound loses sulphur easily, and 

 is difficult to obtain pure. 



Analyses of thiophthaloxime. 



Substance. ^^"aUcTd":' Nitrogen. 



Gram. cc. Per cent. 



0.2015 11.12 7.73 



0.3010 16.52 7.69 



Calculated for CsH.O.NS 7.78 



Substance. ^^^ph^e."'' Sulphur. 



Gram. Gram. Per cent. 



0.2125 C.2455 16.23 



Calculated for C8H5O2NS 17.81 



An alcohol solution gave an absorption spectrum with a clearly 



indicated, although shallow, color band heading at . =2040, a 



small band at r-=3040, and a well-marked band at -=3480. 



A A 



The addition of alkali turned the alcohol solution a purplish 

 red, and the spectrum of such a solution containing 1 equivalent 

 of sodium ethoxide showed a very broad and deep color band 



heading at the same point as before; that is, -=2040, but 



A 



appearing in thousandth molar concentration. 



The band at ~ = 3040 was reduced to a mere fraction of its 



^ 1 



original size, and that at - = 3480 was nearly destroyed. 



