VOl. s2The tan solution was examined by visible-ultraviolet spectroscopy and shown to contain 0.99 mmole of tricyanovinyl alcohol ( A, , , 297 mp, B 11,300) and 0.01 mmole of 1,1,2,3,3-pentacyanopropene (Amsx 397 and 414 mp, e 22,600 and 22,-100, respectively).When a solution of 0.81 g. (5.9 mmoles) of tricyanovinyl chloride in 4 ml. of tetrahydrofuran was treated with 2 ml. of water, a rapid (45 seconds) exothermic reaction took place with evolution of carbon dioxide (identified by the white precipitate it gave with lime water). The addition of 1 .O g. of tetramethylammonium chloride in 15 ml. of water followed by the removal of the tetrahydrofuran under vacuum gave 0.364 g. (51 %) of tetramethylammonium pentacyanopropenide, m.p. 310-312'.The ultraviolet-visible spectrum was identical with that of an authentic sample.
Reaction ofTricyanovinyl Chloride with Tricyanovinyl Alcohol.-A mixture of 1.37 g. (0.01 mole) of tricyanovinyl chloride, 1.92 g . (0.01 mole) of the tetramethylammonium tricyanoethenolate and 15 ml. of tetrahydrofuran was heated under reflux on a steam-bath for 4 hours. The solid that separated weighed 2.33 g. It was shown to contain 0.0068 mole of pentacyanopropenide anion by spectroscopic examination. The filtrate yielded 0.45 g. (3370) of unreacted tricyanovinyl chloride after concentration and sublimation, Reaction of Tricyanovinyl Ethyl Ether with N ,N-Db methylanilme.-A solution of 1.47 g. (0.01 mole) of tricyanovinyl ethyl ether in 5 ml. of N,N-dimethylaniline was heated in a boiling water-bath for 30 minutes. The resultant deep red solution was taken up in 30 ml. of methylene chloride and extracted successively with two 25-ml. portions of cold 2 N hydrochloric acid, 25 ml. of water and 10 ml. of saturated sodium chloride solution. The organic layer was then concentrated and chromatographed on acid alumina (Woelm) using ethyl acetate-acetone for elution. The deep-red gummy solid weighed 0.95 g. and contained 0.74 g. (34% yield) of N,N-dimethyl-p-tricyanovinylaniline as shown by the visible absorption intensity a t 515 mp. The infrared spectrum of this gum indicated the absence of N,N-dimethyl-~-(2,2-dicyano-l-ethoxyvinyl)-aniline ,l*The study of the specificity of ozone attack on unsymmetrical olefins is continued with cis-1,2-dibenzoylpropene, cis-l,2-dibenzoyl-1-methoxyetliylene, cis-l-amino-1,2-dibenzoylethylene and cis-and trans-1,2-dibenzoylstyrene. The results of this study and of studies made elsewhere make it clear that there is no single type of initial ozone attack, nor is there a single route to peroxidic and non-peroxidic ozonation products after the inital ozone attack. With most olefinic double bonds, however, it appears that a five-membered ring intermediate is produced via, a t least in protolytic solvents, a rr-complex involving the terminal electrophilic atom of the ozoiie molecule.