March 20, 1953
1471
NOTES Synthesis of l,J-Diphenyl-1,2,4-triazole BY M. R. ATKISSOS~ A N D J. B. POLYA RECEIVED AUGUST 12, 1952
Anal.'" Calcd. for C14HllXz: C, 76.99; H, 5.01; N, 18.99. Found: C, 76.31; H , 5.33; S,19.18. The triazole and its picrate depress the m.p.'s of authentic I1 and its p i ~ r a t erespectively. ,~
(10) hlicroanalyses by D r . W. Zimmermann, Commonwealth Einhorn, Bischkopff and Szelinski2 reported the Scientific and Industrial Research Organization, Melbourne. preparation of 1,3-diphenyl-1,2,4-triazole (I) from CHEMISTRY DEPARTMENT phenylhydrazine and N-formylbenzamide in 30% UNIVERSITY O F TASMASIA aqueous acetic acid. Thompson3 showed that this HOBART, AUSTRALIA reaction affords 1,5-diphenyl-l,2,4triazole(11) identical with the preparations of Young4 and C1eve.j We were able to confirm the work of The High Field Conductance of an Aqueous Solution of Cadmium Chloride at 25'' Thompson and showed that I1 is obtained, although in inferior yield, when pyridine containing pyri- BY FREDERICK EUGENEBAILEY,JR., AND ANDREW PATTERdinium hydrochloride is used instead of dilute SON,JR. acetic acid.6 RECEIVED SOVEMBER 7 , 1952 It was necessary to synthesize I in order to assess The unusual behavior of cadmium halides in the work of Einhorn and his collaborators as the physical data characterizing their triazole differ aqueous solution has been the basis for much disfrom those which apply to I1 by the agreement cussion in the past.2 Harned and Fitzgerald of other authors. The synthesis of I was accom- found that the behavior of aqueous solutions of plished by the method of Ponzio7 which has been cadmium chloride in electrolytic cells might be adefound useful in other triazole Benz- quately explained3in terms of an equilibrium amide phenylhydrazone heated with formic acid CdCl+ I_ C d + + + C1-; K ( 0 ) = 0.011 a t 25" (1) affords I in a yield of 36y0, I, its hydrochloride i t being assumed that the dissociation of CdClz into CdC1+ and C1- is complete. To investigate iSH2 HCOzH + P h l H N = C ( + H-cHN\C-Ph this electrolyte from another point of view, we have Ph determined the high field conductance of an aqueI /I ous solution of cadmium chloride, 1.697 X 2H20 Ph-IT-K molar, a t 25" relative to potassium chloride. and picrate differ from the corresponding products The procedure employed was identical with that described by Einhorn and collaborators. of Gledhill and P a t t e r ~ o n . ~Baker and Adamson C.P. cadmium chloride was recrystallized once from Experimental conductivity water; the resulting hydrate was Benzamide phenylhydrazone \vas prepared by the method dried for four days in a vacuum oven a t SO", of Voswinkelg and purified through its picrate, m.p. 196198'. Benzamide phenylhydrazone (7.20 g.) was refluxed ground in an agate mortar, and again dried for four with 99% formic acid (8.0 ml.) on the water-bath for 90 days in a vacuum oven a t SO". The resulting salt, minutes. The product was adjusted to @H8 with aqueous assumed to be anhydrous, was then stored for use. 10% sodium carbonate and extracted with ether (3 X 50 Both the cadmium chloride and reference electromi.). Distillation of the dried ether extract between 160220" (2 mm.) afforded oily crystals (4.5 g.) which were dis- lyte, potassium chloride, were prepared by weighing solved in dry ether (150 ml.) and treated with dry hydrogen in the form of strong stock solutions and then weight chloride to precipitate the hydrochloride of I as a white, diluted to the desired concentrations in the conmicrocrystalline powder, m.p. 192-191' (Einhorn, et al., ductance cells. The concentrations were : cad176") in a yield of 5.73 g. Anal. Calcd. for C14H11Na.HCl: mium chloride, 1.697 X molar; potassium C1, 13.76. Found: C1, 13.70. molar. The temperature The hydrochloride was decomposed with aqueous 10% chloride, 2.889 X sodium carbonate (100 ml.) and extracted with ether (3 X was25 =t0.015'. 50 ml.) to afford on removing the solvent colorless prisThe results are shown in Fig. 1 for two determinmatic crystals of I, m.p. 79-81' (2.71 g., 36%). Purificaations on the same solution. At 200 kv./cm. the tion through the picrate, yellow needles from ethanol, m.p. 161-161.5' (Anal. Calcd. for C14Hl1iS3.C~H307N3: C, fractional high field conductance quotient, AA/Ao, 53.33; H , 3.11; N, 18.67. Found: C, 53.35; H, 3.24; has the value 1.0770; this value may be compared N, 17.67) (Einhorn, et al., 148") and two recrystallization: with those for potassium chloride, approximately from petroleum ether (60-80") raised the m.p. to 82.5-83 O.4yO,and magnesium sulfate, approximately 3.370, (Einhorn, et al., 96-97'). a t the same field. No theory is currently available (1) Imperial Chemical Industries of Australia and New Zealand to permit computation of values for non-symmetriResearch Fellow. cal valence-type electrolytes, although as a rough (2) A. Einhorn, E . Bischkopff and B. Szelinski, A n n . , 343, 227
+
(1905). (3) Q.E. Thompson, THISJOURNAL, 'IS, 5914 (1951). (4) G. Young, J . Chem. Soc., 61, 1069 (1895). ( 5 ) A. Cleve, Be?., 29, 2679 (1896). (6) (7) (8) (9)
M. R. Atkinson and J. B. Polya, J . Chem. S o c . , in press, (1952). G . Ponzio, Gaze. chim. ital., 40 i , 85 (1910). D . Jerchel a n d R. K u h n , A n n . , 668, 185 (1950). H. Voswinkel, Ber., 36, 2484 (1903).
(1) Contribution No. 1133 from t h e Department of Chemistry, Yale University. (2) N. V. Sidgwick, "The Chemical Elements a n d Their Compounds," Oxford University Press, New York, N. Y . , 1950, p. 274. (3) H . S . Harned and B. B. Owen, "The Physical Chemistry of Electrolytic Solutions," 2nd ed., Reinhold Publ. Corp., New York, N. Y., 1950 pp. 418-421. (4) J. A. Gledhill and A. Patterson, J . P h y s . Cheiii., 66, 999 (1952).
