3018
J. H.UOYEK .ZND L. li. MORGAN, Jri.
815' (214-216°).1s 11 iiii.\lure iiielting point with an authentic sample of the hydrochloric acid salt of beiizylphenylxinine, m.p. 214.&216', melted at 213-215'. Reaction of N-Nitrosodibenzylamine with Lithium in Liquid Ammonia.-To a stirred solution of 1.54 g. (0.22 g . atom) of lithiuni dissolved in 250 nil. of liquid ammonia was added dropwise a solution of 10.0 g . (0.044 mole) of N-nitrosodibeiizylamine in 125 ml. of dry ether and 25 ml. o f dry dioxane. External cooling was removed and after 10 minutes color change from blue to white tlicn from orange to bright red was observed. The red reaction wa5 stirred for 1.5 hours and then hydrolyzed with 50 nil. of ethanol followed by 50 ml. of water. The reaction mixture nas poured into 500 nil. of water, extracted with ethcr arid the extracts dried over magnesium sulfate. Removal of solvciit yielded 2.0 g. of rcsidue. At this point, in another exlmimeiit, 6y6 of tribeiizylhytlraziue, m.p. 82.5-84" (n1.p. 86")8was isolated by crystalli. . zation from the residue. A picrate salt was prepared in ether, n1.p. 138-140.5 (m.p. 140-141°).8 The mixture was extracted with dry Skellysolve l3 several times and the extracts chromatographed through neutral alumina ( Woelrn, activity one). -4 Skellysolvc B-illsoluble material was recrystallized froin ethanol, 0.50 g., 1ii.p. 205207". This solid contains iiitrogeii and an infrared spectrum exhibited a strong absorption a t 6.0s b , probably C=K.Ig The solid reacts slowly with a rnethamolic hydrochloric acid solution of 2,4-diriitroplieriylii)-tlrazineto give (18) W ,S. Emerson and 1'. A I . Waltcrs, 'TJIIS J U U I < N . U . , 60, 2023 (I'J38): K. Brand, Her., 42, 3400 (IOOS). (I!)) 1.. J. Bellamy, "The Infrared SlJectra uf ~ ~ ~ I l I ~ hlulccules." J l e x J u l i n \Vile? a n d Sons, Inc., S e w Yijrk, X . Y . , 1951, 11. 221;.
VOI.
so
an orange derivative, ri1.p. 118-131". The sulid was 1101
further characterized. The first 25-ml. fraction obtaiiietl from the columii, usiiig dry Skellysolve B as eluent, yielded 0.32 g. ( 4 % ) of hibenzyl, m.p. 50-51.5'; a mixture melting point with iiuthentic bibenzyl melted a t 60-52". The iiext three fractions yielded 1.75 g . (37.5%) of benzylainine, whosc picrate salt prepared in ethcr, melted at 197-200" ( 195-199°).2t' '1 mixture ineltirig point with the picrate salt of authetitic benzylarnine melted a t 197.5-200'. A yellow band was removed from the column, using dry methanol its cluellt, yielding 1.3 g . (15%) of dibenzylamiric, whose picrate sult prepared in ether melted at 139-141". 1 1 mixture iiieltiiig point with the picrate salt of authentic dibciizylarniiie prcpared in ether mclted a t 138.5-140°. The picrate salt of authentic dibenzylaniiiic was prepared b y adding excess saturated picric acid in ethcr t o an ethcr solution of the amine. Three separate preparations of this salt using various samples of dibenzylamine all yielded t: >-ellow solid, m.p. 140'. The previously rcported8 picratc of dibenzylamine could iiot be duplicated. .In analytical sample was prepared by recrystallization from cthanol to yield yellow needles, i n p . 140-141' (93-94").* Calcd. for C2oHlsSaO7: C, 5G.34; 1-1, ,L.25; S . 10.14. Foutid: C, 56.48; H, 4.61; N, 13.19.
Acknowledgment.-We wish to gratefully ac' knowledge the support of this work by the National Science Foundation, Grant NSF-1433. (20) G. J e r u s a l e m , .I. C/ic,m. Suc., 95, 1283 (1009). 121) S n u l y s e s I)? Schivarzkopf 1 , a b ~ r r a t o r i r hS. c w E'ork,
N. 1'
UIWOKLYN 1, S.Y .
O l C CIiEMISIIIY, 'YULANE U N I
Pyrolysis of Pyruvic Acid Hydrazonesl I3Y
5. 13. I3OYEIi A N D L. 1
