4104
C.G. OVERBERGER A N D BURTONS. MARKS
bined with the organic layer :md dried over ailhydrous potassium carbonate. Removal of the solvent under reduced pressure and nitrogen gave a mass of pasty, brown crystals which were recrystallized twice from "Skelly A" to givc 16 g. (72.5%) of a yellow crystalline material, m.p. 4649". An analytical sample was prepared by successive recrystallization followed by chromatographing on alumina followed by recrystallization, m.p. 51.5-52.0" (52O, no yield reported from diacetosuccinic ethyl ester and hydrazine followed by saponification and decarboxylation27) ( 5 2 ', from acetonylacetone and the formsd derivative of hydrazine followed by saponification, no yield reported23). Anal. Calcd. for C ~ H I O KC~, :65.41; H, 9.15; N , 25.43. Found: C,65.34; H,9.21; N,25.12. Benzoylation of 1-Amino-2,S-dimethylpyrrole.--A benzoyl derivative was prepared by treating 2.25 g. (0.02 mole) of 1-arnino-2,5-dimethylpyrrolewith benzoyl chloride in pyridine29 to obtain 2.1 g. (49%) of crystals, m.p. 178-183". Recrystallization from 85% ethanol gave crystals, m.p. 184185.5". A mixed melting point with a sample prepared according to the procedure described in reference 11 was not depressed, m.p. 180-182' (177-179", no yield, from SaminoDvrrole2') 1184-185", 60-66%,.from reaction of acetonylacetone with benzoyl derivative'Gf hydrazine"). Reduction of 1-Amino-2,s-dimethylpyrrole to 1-Amino2,S-dimethylpyrrolidine.-Hydrogenation of 11 g. (0.1 (27) C Bulow, B e y , 36, 4311 (1902). f28) E E Blame, Compl r e n d , 174, 221 tlQ21) (29) Reference 21, p 177.
Azo Compounds. BY
1'01. 77
inole) of l-a1nino-2,3-dimetl1yIpyrrole i i i 05 1111. of gluckil acetic acid with 2 g. of 5% rhodium on alumina catalyst wa5 carried out a t 3 atmospheres. Hydrogen absorption amounted to 112%, based on two double bonds, a t rooin temperature in 2 hours. The catalyst was removed, t11c solution made basic with potassium hydroxide, and theti extracted with methylene chloride. The extract was dried over anhydrous potassium carbonate and the solvent rcmoved under reduced pressure to give 10 g. of a brown liquid. Distillation resulted in 4.5 g. (39%) of l-arnino-2,S-dimethylpyrrolidine, b.p. 36-37" (13 mrn.), X ~ 1.4488. ~ D A picrate was prepared from a solution of picric acid i i i ether, m.p. 154-15Fj0 dec. A mixed melting point with tlic picrate prepared by the hydrogenation of the S-nitroso compound melted a t 154-156" dec. The tetrazene was prepared by oxidation with potassium permanganate as described previously, m.p. 43-44 '. A mixed melting point with the sample prepared by oxidation of the S-amino product froin reduction of the nitroso intermediate melted a t 41-43 '. Infrared Spectra.-A Perkin-Elmer niotlcl21 double beaiii recording spectrophotometer was employed witli a NaCI prism to study the 2-15 A, range.
Acknowledgment.-iVe wish to gratefully 'ICknowledge the support of this work by the Ofice of Ordnance Research, Contract No. DA 30-069ORD-1158. RROOKLYS,S. Y
Oxidation Studies of 1,l-Disubstituted Hydrazines]
c. G .
O T ' E R B E R G E R AND B U R T O N
s. - \ I A R K S '
RECEIVED MARCH 4, I955 The oxidation of 1,l-dibenzylhydrazine with bromine in ethanol and w i t h !-butyl hypochlorite folloiveti by reaction tvith base has been studied. Two reaction paths are proposed, one to form bibenzyl by an unusual nitrogen elimination and two, the formation of a tetrazene and its decomposition products, benzylamine, dibenzylamine and benzaldehyde. From thc bromine oxidation, ethyl benzoate was also isolated. From the oxidation with the hypochlorite in addition t o normal prodwith permanganatc ucts some tribenzylhydrazine was found. The oxidation of l-amino-2,6-dicyano-2,6-dimethylpiperidine mas examined and the products compared with the previously reported bromine oxidation of the same compound. It i, concluded that resonance stabilization of the intermediate after loss of nitrogen favors the abnormal reaction, that is, nitrogen elimination without tetrazene formation.
A large number of oxidations of 1,l-disubstituted hydrazines are recorded, many of which were reported by These oxidations were carried out with commonly employed oxidizing agents, including benzoquinone, potassium permanganate, bromine, sodium hypochlorite, ferric chloride, mercuric oxide, etc. -1tetrazene was the usual primary product. -1sa result of a review of this previous work, two anomalous results from these oxidations were noted. The first example was reported by Rusch and lTeiss4 who treated 1 , l -dibenzylhydrazinc with mercuric oxitlc a n d obtained bibenzyl as thc (1) This is t h e 14th in a series of papers concerned with the preparation and decnmpnsition of azo compound For t h e previniis paper in this serieb. see C (;, Ovcrbergrr. I. < Palrrrrr, B 5 7r.irk. :m1 N K . B y r d , THISJ O U R N A L , 77, 4lOU i I Y . 5 3 ) . ( 2 ) This paper comprises a portion of a thesis presented b y B 5 . &larks in partial fulfillment of t h e requirements for t h e degree of Doct o r of Philosophy in the Graduntc School of the Pnlytechnlc Institute ~ r lB r o o k l y n . ( 3 ) H . \Vieland, "Die II>drarine," Verlai. roil l ~ e r d i n ~ t l il li l ~ k e . ititttRart. 1 4 1 3 , p p H8, :{!I , I ) 11 Husch ani1 13 \Yeis\ !;v, , 3 3 , "(11 ii')00r
oiily product alorig with the theoretical evolution of nitrogen. Curtius and Frarizenj perfortnecl thc same oxidation with mercuric oxide, using as a solvent, instead of ethanol, chloroform. They obtained, in good yield, tetrabenzyltetrazene, and do not report any bibenzyl. lVieland6repeated this oxidation and obtained small amounts of tetrazene aiicl largely bibenzyl. M i c h a e l i ~ ~treated .~ 1-allyl-1-phenylhydrazine with mercuric oxide and obtained instead o f the e s pected tetrazene the rearranged benzeneazopropene-2, indicative of a type of allylic rearrangement. If, however, ferric chloride was used instead of incrcuric oxide, then the expected tetrazene was 01)tained.7 Similarly, 1-allyl- 1-p-tolylhydrazine reacted with mercuric oxide to give p-tolylazoproperie-z8 but yielded the tetrazerie with ferric chloride. Bromine oxidation of a compound reported to ( 5 ) T.Curtius dnd H. Franzen, ibid., 3 4 , 5 2 2 ( l ! N I l ~ . (I?) H . Wieland and H. Fressel, A n n . , 394, 133 ( I R I ? ) $ 7 ) 1 lfichnelis a n d C Claeisen, A?;. , 2 2 , 22:i:i (!88!l , 3' A X1ich;ielis am1 ! 1~x=s~
