L'iO?
C. 1;. H. ALLENAND J. W r . GATES,JR.
ir01. 65
.irzal. Calcd. for CisHlaN&: Tu', 15.0. Found: N, i-k.85. XXIV was comparatively stable to 2% sodium hydroxide. Under the conditions described for the hydrolysis of XXa, the m. p. %'as only lowered to 190-195" dec.
.~-Phenyl-5-acetoxypyrazole,VI, 1-acetyl-3-acetoxp-3-phenylpyrazole, IX, 1-acetyl-3-hydraxy3-phenylpyrazole, IV, 3-phenyl-5-benzoyloxypyrazole, X, l-acetyl-3-phenyl-3-benzoyloxypprazole, XI, I-benzoyl-3-phenyl-5-benzoyloxypyl-Benzoyl-3-anilino-5-benzoy~oxypyrazole, XXV.--A mixture of 5 g. of 3-anilino-5-pyrazolone, XVI,1*4 and 4 g. razole, XIV, 1-benzoyl-~3-benzoyloxy-3-phenylof be~izoylchloride in 50 ml. of dioxane was stirred on the pyrazole, XV, 1-acetyl-3-hydroxy-5-anilinopysteam-bath overnight. After cooling, the solution was razole, XVII, l-acetyl-3-anilino-5-pyrazolone, tieranted from a n oil, diluted with water ( 5 ml.) until XXa, l-acetyl-3-anilino-5-acetoxypyrazole, XXIa, cloudy, cooled, filtered, and the product recrystallized from l-acetyl-3-acetoxy-3-anilinopyrazole, XXII, .iiT, tnl. of dioxane. I g. (13y07,) of short ivory needles; ni. p. ::32--134 anilino-3-benzoyloxypyrazoleIXX, 1-benzoyl-3 A n n i . Calcrl. for C-i;sH:;N~O;%: S,10.9;. Found: K, anilino-5-pyrazolone, XXIV, and l-benzoyl-% I I I. $14, ..i h e oil formed in the reaction mixture, on trituration anilino-5-benzoyloxypyrazoIelXXV, were pre pared as new compounds and their structures first with water and then methanol, gave 0.6 g. of unestablished. changed 3-anilino-5-pyrazolone XVI.'? Pure l-acetyl-3-phenyl-3-pyrazolone, 11, melts Film-strip Test.--A sample (about 0.005 9.) of the compound to be tested and a n approximately equal weight of a t 127'. The compound reported in the literature p-aniinodimethylaniline hydrochloride are dissolved in 5 as melting a t 121' is contaminated with VI. The ml. of 3% sodium carbonate in a test-tube. A strip of diacetyl derivative of 3-phenyl-5-pyrazolone meltexposed photographic film ( e . E . , Rodalithj is immersed i n the solution and the test-tube shaken occasionally until, ing a t 8-1' is not 1,2-diacetyl-3-phenyl-5-pyrazowithin one t o five minutes, a high density of silver is de- lone, VII, but l-acetyl-3-phenyl-5-acetoxypyraveloped. The strip is then rinsed with running water for d e , V I I I . about one minute, and silver and silver halide are removed A migration of acetyl from nitrogen to oxygen hv shaking the strip in a mixture ( 5 ml. total) of equal was found to occur when 1-acetyl-X-phenpl-.jparts of solutions 1 and 2 . until the film is translucent. It pyrazolone, 11, was treated with pyridine, yielding i.s then washed in running water and inspected. 3-phenpl-5-acetoxypyrazo1el VI. Solution I : 25 g . uf potassium ferricyanide, 5 g. of potassium bromide, 5 g. of sodium carbonate, water to A migration of acyl from position 1 to position make 1 liter. Solution 2 : 200 g. of sodium thiosulfate, 2 was observed with several of the above-named ,i g of sodium carbonate, water to make 1 liter. pyrazoles. Summary The formation of dyes by color develop The acetylation and benzoylation of 3-phenyl- ment of a photographic film is described as a 5-pyrazolonc, I, and of 3-anilino-5-pyrazolone, test XST. were studied I
