COMMUNICATIONS TO THE EDITOR
May 20, 1957
266 1
m.p. 123-124', [a]"D +76" (c 0.91, CHCl,). a potential source of the biradical 1,4-diphenylH~ Anal. Calcd. for C l ~ H ~ 3 0 9 NC, : 49.86; H, 6.42. 1,4-butadiyl (11) C ~ H & H C H Z C C H Z H C ~which Found: C, 49.71; H, 6.45. Catalytic deacetyla- is of interest as possibly being formed by interaction of I11 with barium methylate afforded methyl tion of two molecules of styrene monomer during 2-acetamido-2-deoxy-a-~-gulopyranoside (yield thermal polymerization. Compound I is analogous to the acyclic azo compounds' (111) R = CH, or 7270) ( I v ) , m.p. 79-82', [ a I z 6 D +72O ( C 0.74, CHIOH). Anal. Calcd. for CgH1708N: C, 45.9,5; R R H, 7.29. Found: C, 45.80; H , 7.22. A crystalC6~5-CH-??=N-C~-C6l~6 I line 0-benzylidene derivative was prepared, m.p. 111-114', [a]"D +71° (C 0.90, CHIOH). A n d . Calcd. for ClsHZlOEN: C, 59.43; H, 6.55. Found: C&, which lead to styrene-type radicals. AtC, 59.08; H, 7.07. 2-Amino-2-deoxy-~-gulosehy- tempts to prepare a six-membered cyclic azo comdrochloride (D-gulosamine hydrochloride) (V) was pound analogous to azo-bis-iso-butyronitrile2failed, obtained in a 66y0 yield by treatment of IV with apparently because of thermal instability. A hydrochloric acid, 1,70-170° dec., [a]"D t 6 . 1 " (10 previously reported3 synthesis of I had in fact led min.) + -17.9" (36 hr.) (c 0.90, H20). Anal. to the hydrazone-type tautomer4 (117) Calcd. for CeH&NCI: c , 33.26; H , 6.48; N, 6.50; C1, 16.44. Found: C, 33.47; H, 6.56; N, 6.32; C1, \ CsIIs-cH/CH*-cH* 16.52. A crystalline derivative was prepared, 2C-C6115 deoxy-2- (2'-hydroxynaphthylidenamino)- D - gulose, \NH-N/ m.p. 186-188" dec., [ a I Z 2 6 4 6 1 - 150" (at equilibrium, c 0.60, methyl cellosolve). Anal. Calcd. for Cli- Xmax 292 mp, log E 4.19. Compound I was prepared by (1) addition of diH L 9 0 6 N :C, 61.26; H , 5.75. Found: C, 61.16; H , 5.8G. The structure of V was ascertained by ethyl azo-dicarboxylate to 1,4-diphenylbutadienedegradation with ninhydrin in presence of pyridine4 1,3, forming the adduct, 1,2-dicarboethoxy-3,695% yield, to D-xylose, identified by paper chromatography. diphenyl-l,2,3,6-tetrahydropyridazine, Chromatographed on paper in the mixture n-pro- m.p. 134-136", reported5 132' ; (2) hydrogenation panol-ammonia 1% 70:30, V migrated 1.18, com- of the adduct to the hexahydro derivative, 70% pared to D-glucosamine 1.OO, D-galactosamine 0.91, yield, m.p. 85-87', reported5 87"; (3) saponificaand D-allosamines 1.03. Treatment of V with pyr- tion with potassium hydroxide and decarboxylaidine and acetic anhydride, followed by reflux with tion in boiling methanol under nitrogen, and aumethanolic hydrochloric acid and subsequent reace- toxidation during concentration of the dried ether tylation of the crude product with pyridine and extract, 22% yield, decomposing with vigorous gas acetic anhydride, gave a compound, m.p. 116- evolution when placed in a bath a t 120°, Amax 287 119", [ a I 2 I D -54' (CHCI,) to which the structureof a mp, log E 3.49, Amax 387 mp, log E 2.89. Anal. Calcd. for C16H16N2: C, 81.30; H, 6.82; N, 11.85. methyl 2-acetamido-3,4,6-tri-o-acetyl-2-deoxy-p-~gulopyranoside (VI) was attributed on the basis of Found: C, 81.48; H, 6.92; N, 11.7,5. The abthe sequence of reactions, rotation a n d analysis, sorption due to the azo linkage is displaced from its normal position at about 350 to 387 mp, apFound: C, 49.69; H, 6.5s. A sample of natural gulosamine.6 chromato- parently because of the cis configuration of I, graphed on paper had the same Rfvalue as V. Sub- acyclic aliphatic azo compounds normally having mitted to the above described treatment, it gave a the trans configuration about the azo-linkage. compound, m.p. 116-119", [ a I z 3-53", ~ showing Compound I is tautomerized readily to IV, by heat or by polar solvents. no depression of the m.p. in admixture with VI. Thermal decomposition of I in dilute solution in (4) P. J. Stoffyn and R. W. Jeanloz, A r c h . Biochem. B i o p h y s . , 62, 373 decalin a t 136 and loo", in ethylbenzene a t looo, (1954). and in 3.46 moles/l. styrene in ethylbenzene a t (5) R. W. Jeanloz, THISJOURNAL, 79, 2591 (1957). (6) We are very grateful t o Dr. John R. Dyer, Georgia Institute of 100" and a t 80" leads to essentially quantitative Technology, Atlanta, Georgia, for providing a sample of natural Devolution of nitrogen. Thermal decomposition of gulosamine hydrochloride. solid I leads to partial isomerization to I V ; styrene ROBERT W. LOVETT MEMORIAL LABORATORIES is formed as one of the products of decomposition MASSACHUSETTS GENERAL HOSPITAL, A N D THE of solid I, identified as the dibromide, m.p. and DEPARTMENT OF BIOLOGICAL CHEMISTRY HARVARD MEDICAL SCHOOL mixed m.p. 68-70', reported6 72-73'. The deZOFIA TARASIE JSRA BOSTON15, M A S S . ROGERW. JEANLOZ composition in solution a t 80" had a half-life of RECEIVED FEBRUARY 21, 1957 about 20 minutes and appeared about 100 times as fast as that of the acyclic analog1 111, due apparently to the cis nature of the cyclic compound A CYCLIC AZO COMPOUND, 3,6-DIPHENYL-3,4,5,6- and possibly in part due to concomitant formation TETRAHYDROPYRIDAZINE (1) .. of the styrene. A large (24membered) ring bisSir: (1) S. G. Cohen, S. J. Groszos and D. B. Sparrow, THISJOURNAL, 72, We wish to report the preparation and decom- 3947 (1950). position of the six-membered cyclic azo compound (2) C. G . Overberger, N. R. Byrd and R. R. Mesrobian, ibid., 78, 1961 (1956). (1) CsH5-CH
/C11i-cH2
"=NI
\
CHCakl5
(3) A. P. J. Hoogeveen and C. V. van Hoogstraten, Rec. f r a u . chi77z., 62, 378 (1933). (4) S. G.Cohen and C . H. Wang, THISJOURNAL, 77, 2457 (1955). (5) K. Alder and H. N k l a s , Anla., 686, 81 (1954). (6) R. Fittig and E. Erdmann, ibid., 216, 194 (1883).
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COMhIUNICATIONS TO T H E
Vol. 79
EDITOR
with gas evolution, A,, 290 mp, log E 2.21, Amax 389 mp, log E 2.03. AnaZ. Calcd. for C17Hl&T2: C, 81.56; H, 7.25; N, 11.19. Found: C.81.51; H, 7.01; N, 11.23. Air oxidation of the crude hydrazine has also yielded the azo compound. The normal azo absorption found in acyclic azo compounds a t approximately 350 nip," has becri displaced t o 389 mp, presumably due to the cis configuration forced on the azo link in I, IZ = :i. Thermal decomposition of I, n = 3, in xylene solution at 100.2" gives first-order kinetics, half-lii'c 2.9 minutes, with a 94yo evolution of nitrogen ( 7 ) C. Overberger and 11,Lapkin, THISJ O U R N A L 77, , 4651 (1955). after 31 minutes. Decomposition of I in xylene a t SCHOOL OF SCIENCE CHI HUAWANG 80" gave a half-life of 27.1 minutes with oiily a BRANDEIS UNIVERSITY SHU-HSIHSIAO \VALTHAM 54, MASSACHUSETTS EUGENESAKLAD 71.5% evolution oi nitrogen. These decomposiSAULG. COHEN tion rates are over 100 times faster than the corresponding linear trans3 azo compounds. -4nalysis RECEIVED FEBRUARY 12, 1957 of products of the decomposition a t SO" indicates 290 the presence of the hydrazone 11, n = 3, A,, SEVEN- AND EIGHT-MEMBERED RING AZO COM- mp, log E 3.60. Analysis of the ultraviolet spectrum POUNDS of I , n = 3, has shown that I slowly isomerizes to Sir : the hydrazone IT, n = 3, in ethanol a t rootn temWe wish to report the synthesis and aecomposi- perature. tion of the azo compounds (I) The synthesis of the eight-membered ring azo compound I, n = 4, was carried out by preparing the appropriate cyclic azine by a modification of CtiHj-CH 'CH-GH~, n = 3,4 the method of Overberger and Lapkin,4 m.p. 136's=A-' 737", Xma,268mp, log €4.45. Anal. Calcd. for CIYDecomposition of these cyclic azo compounds HlsNz: C, 8 . 4 2 ; H, 6.92; X > 10.68; mol. wt., 262. should provide biradicals of the benzyl type. The Found: C, S2.64; H, 6.90; N, 10.13; iiinl. w t . preparation of the six-membered ring analog is also 281 (ebullioscopic in butanol). Quantitati\-e rcdescribed in this issue.' d method for the prep- duction of the aziiie followed by immediate osit1:iaration of the hydrazine precursor of I, n = 3, by tion with mercuric oxide yielded 575% of I, ?z = - 4 , reduction of the azine with lithium aluminum hy- 1n.p. SS-9O0, A,, 368 inp, log E 1.63. Anal. Calctl. dride has been reported previously.2 As a pre- for C1BH20N2: C, 81.77; H, 7.63; N, 10.60; mol. parative method, this procedure is unsatisfactory wt., 264. Found: C . 81.60; H, i . 4 i ; S ,10.7;;; owing to the formation of the hydrazone (11) mol. wt., 297 (ebullioscopic i i i butancil).~ 'The illfrared absorption for both I , ?z = 3,1,are almost identical, show n u hydrazone absorptions and COP firm the conclusions made from ultraviolet data. c~H~--cH' C-C6HSr 11 = 3 Acknowledgment.--1Ve wish to thank the Na\ NH--N / / tional Science Foundation for the support of :L A,,, 200 mp, log E 3.73, from incomplete reduction portion of this work, Grant NSF-1433. of the azine and from isomerization of the azo f;il S. ,.C Cclheii, 5 J ( ' , n > > z n ?nnd U. H S!>,trro!v, L b i L 7 2 , 39-47 compound obtained by autoxidation of the hydra- (19zn). 84j C . yl) d e r i v a t i v e (rf I , = 4 over lOyo palladium-on-charcoal followed by immediate oxidation of the crude hydrazine with I ) E P A R r M E S T O F CHEXISTRY C. G . OVERBBRGEK JOSEPH G . LOMB.4RDIKO ISSTITUTE01: mercuric oxide gives %.4y0 of I, n = 3, m.p. 115", POI,\-TECHSIC
azo compound7 has been reported, with ultraviolet absorption maximum and rate of decomposition quite similar t o those of the acyclic analogs,l the size of the ring apparently allowing the azo linkages to assume the trans configuration. Decomposition of 0.036 mole/l. of I in 3.46 moles/l. styrene in ethylbenzene a t 80" led t o polymerization of 8.5 molecules of styrene per molecule of I. Acknowledgment.-We are pleased to acknowledge generous support of this work by the National Science Foundation (NSFG575).
,
,l
(1) C . H. Wang, S. Hsiao. E. Saklad aud
7 9 , 2661 (19.573. ( 2 ) C. G. Overberger a n d
S G. Cohen, THISJ O U R -
NAL,
1.J.
Ilonagle, i b i d , 78, 4470 (1956).
BROOKLYS
IR~ISG TASHLICK
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