The sjm-trinitrobenzene complex separated froiii 1)etizvne -iiiethanol as bright red needles, t n . p . 210~-211'. / 1 n d . Calcd. for C?iHl,06;\;3: S , 8.76. riotinti: S,
Elution with a second 100-nil. portion of hexane afforded 40 xng. of the ethylidene compound XI11 as needles from ~rans-ll-Ethyl-1,2,3,4,4a,l2a-hexahydrochrysene (XII) methanol, m.p. 116-1t7', depressed t o 90" oii adniisture and trans-1 l-Ethylidene-l,2,3,4,4a,11,12,12a-octahydro-with trans-l,2,3,4,4a, 11,12,12a-.~ctaliydrochrysene, til . 1 i . chrysene (XIII).--A Grignard solution prepared from 0.24 115-116" (see above). 'The ultraviolet absorption specg. (0.01 g. atom) of magnesium and 1.6 g. of ethyl iodide in trum (Amax (log e ) : 238 nip (4.86), 315 (4.04), 328 (3.86 I 20 t n l . of dry ether was added dropwise, at O", to a stirred and 336 (3.87)) as in ncct)rtl with t h e structure assigned t i l solutioti of 0.75 g . (0.003 mole) of the keto chrysene I in 20 this hydrocarbon. i i i l . of dry benzene. After stirring a t ordinary temperature A n d . Calcd. for C1,,f122:C , 91 .(:I); 11, 8.40. I ~ ~ ~ i i t i < l : fiir 2 lir., the solution was heated under gentle reflux f u r 2 C , 92.0%;H, 7.84. lit. :iritl decomposed with dilute hydrochloric acid. T h e tistiti1 w~itkupafforded 0.8 g. of solid material which was deElution of the c1itoni:itcgrapliic colu~riiiuitli 5 0 : 50 I W I I zene-hexane :tffottled 0.5 g. of unte:tcted ketoiie I , ii1.1). 123 ( 2 0 ) .4fter the submission of this paper we were informed of t h e X..%.
\ y n t h c s i s of 7-tnethyl-3,4-henzpyrene and i t s picrate (Ph.D. di5sertation of J m e p h 1. Comp, University of New hleaico. 1956). T h e properties of t.he hydrocarbun, m p, 19O-10lo, and the picrate, purple are in excellent agreement with those reneedles, m.p. 187-187.5', purted here and t h e ultravidet absorptiuii spectrum of the two hydrocarLi,ns were essentially identical. N'e are grateful tu l'ruf. P.iiidc If. 1),11111 iur i h i i illlormation prior t o its piihlication.
[ C ' O N I . K I R L T I O N F R O M THE DAKER
124O. \f*licii both of these Iiytlrocatl~ons(XI1 :itid S I 1 1 were heated to 300-320" with 10' ~~allatliuiii-tiii-charconlcat:ilyst as described above, there \vas o1)tniiietl as the ( ~ i i l y isolalile product L: siiixll > ivltl o f rlir! s t ~ i v ,i i i . ~: i)i i i.I tiii\-t.cl m . p . 230-251".
I IFIACA,
s E \ \ . \'l.lRK
LABORATORY OF CHEMISTKY,
CORSEI.1, r S I V E R S I T Y ]
Polynuclear Aromatic Hydrocarbons. X. The Synthesis of 6,7-Acebenzo [c]phenanthrene 131. 1 ) 0 X A I , I )
n.PIIILLIPS'
AND
I
Tfn,lJiirg I C hriri 5or
12'4 1 i i ' I i 7 ~
{I (1
hug. 20, 19,iS
4365
SYNTHESIS O F 6,7-ACEBENZO [C ]PHENANTHRENE
CHART1
vI
CHCO~R R?/ XI
tone ring in I1 was sucdessfully hydrogenolyzed by the Clemmensen method and the mixture of acids so obtained was separated into V and the corresponding cis isomer, m.p. 158-160' and 219-220°, respecti~ely.~When the trans isomer V was cyclized by hydrogen fluoride, a ketone with identical properties to the I previously reported5 was obtained,s thus establishing its structure. Ketone I condensed smoothly and in high yield with ethyl bromoacetate in the Reformatsky reaction to afford VI (R = C2H6),uncontaminated by any of the endocyclic isomer. When VI was catalytically reduced, one of the isomers corresponding to VI1 was obtained in a pure condition but the major product was a mixture of the two possible isomers. The pure compound and the mixture were both converted to X I by the route described below with essentially the same results, although the yields were corresponding better, as expected, when the pure isomer was employed. The cyclization of pure VI1 afforded one of the isomeric forms of VIII, m.p. 164-165", whereas the mixture of VI1 and its isomer yielded as the principal product the other stereoisomeric form of VIII, m.p. 168-169". The loss on crystallization of this latter isomer was rather high, however, and the mixture from which it was obtained, m.p. 125-130°, was employed in future operations. When ketone VIII, m.p. 164-165", was subjected to the Wolff-Kishner reduction, the corresponding hydrocarbon IX, m.p. 127-128', was obtainedin good yield. The same reduction of the 125-130" mixture of VI11 afforded some of the 127-128' compound as well as the other isomer of IX, m.p. 109-110". (7) Klibansky and Ginsburg6 report m.p. 84-86O for V. (8) About 15% of an unknown ketone was also obtained in this reaction but was readily separated by careful fractional crystallization to afford I as colorless plates, m.p. 154-155', Amax. 5.95 p . Klibansky and Ginsburg6 cyclized their V in the same manner but did not report the isolation of any other product except I which they describe as a yellow oil, Amax. 5.85 u. We find these properties difficult to ascribe to a ketone with structure I and can only assume that the Israeli authors were dealing with a mixture. (Other discrepancies in products derived from I are recorded in the Experimental section.)
The dehydrogenation of I X proved to be very difficult as complete destruction of the hydrocarbon occurred in our earlier experiments. We had anticipated some dificulty with this dehydrogenation in view of the unsuccessful efforts t o synthesize XI from an isomeric hydrocarbon (XII).g However,
nn XI1
XI11
XIV, R = H XI', R = CH3
when I X , m.p. 127-128", was heated to 300-310" for one hour with 10% palladium-on-charcoal catalyst, the desired hydrocarbon X I , m.p. 125126", was obtained in 10% yield. Considerable fragmentation must have occurred during the dehydrogenation as X I was the only hydrocarbon that could be isolated except for a small amount of unreacted starting material. The results with the 109-110° isomer of I X were essentially the same except for the isolation of a small amount (27,) of 3,4-benzpyrene (XIII) along with XI. The formation of XI11 may be ascribed to the presence of trace amounts of @-substitutednaphthalenes in the starting materials as these have recently been shown to serve as convenient intermediates for the preparation of XIII.l0 It may be seen from Fig. 1 that the ultraviolet absorption spectrum of X I , although similar in many respects to the parent hydrocarbon, benzo[clphenanthrene (XIV) , is distinctly different in some regions. The most striking difference may be (9) L. F. Fieser, M. Fieser and E. B. Hershberg, THISJ O U R N A L , 88, 1463 (1936), report that complete destruction of XI1 occurred when heated with selenium, sulfur or platinum. We obtained similarly discouraging results when the corresponding alcohol X was dehydrogenated. (10) D. D. Phillips and D. S. Chatterjee, ibid., 80, 4360 (1958).
3366
DONALD D.
PHILLIPS AND
D. N.
CHATTERJEE
I7ol. 80
F Iir. at rooill temperature, tile re:ictioli iiiiutcire \vas tlcconiposed and the organic material \vas estrarteil wit11 ether. The semi-solid residue left after evaporation of the solvent was saponified by heating for 3 hr. with 8 g. of potassiuin hydroside in 100 ml. o f niethanol. The solvent was reiiioved under reduced pressure aiitl dilution of tlie viscous solution with a large volume of water led to the separation of a large amount of naphthalene and other neutral miterial which was extracted with ether. Acidificatioii of the ctlkaline solution afforded 9 g. of acidic material wliiih \vas tlistilled to give 2.2 g. of cvclohex-anoiie-8-ncetic acid, b.p. 125-130' (0.1 mm.), followed by 6.5 g. of a viscous oil, b.p. 195-200O (0.1 Inm.), which slowly solidified on trituration with a little hexane. Crystallizatioii froin ben\ /' ; zene-hexane afforded 3.2 g. (14%) of the lactone 11 as color-0ENZOlC)PHENANTHRENE (XIVI less plates, m.p. 131-133". An analytical sample crystallized as plates from methanol, m.p. 133-134', A,,,,, 6.68 p , Anal. Calcd. for Cls111802:C , 81.20; H, 6.7C. Foiind: C , 81.29; H, 7.05. 740 760 280 300 320 340 360 380 400 2-a-Tetrylcyclohexaneacetic Acid (HI).--In a11 electriX mo. l m i r 1. cally heated hydrogenation flask were placed 0.5 g. of the lactone 11, 0.1 g. of 10% palladium-on-charcoal catalyst and Fig. 1 20 nil. of absolute ethanol. The mixture was shaken for 10 hr. at 60' under a hydrogen pressure of 43 111. T h e noted in the intensity of the bands from 342 to catalyst was filtered and the solution was evaporated to a 399 mp which have loge values that are larger by a solid residue v, hich was warmed with sodium carbonate unit or more than those of the unsubstituted hy- solution. Extraction of the alkaline solution with ether gave 0.1 g. of unreacted lactone. .-lcidification of the alkadrocarbon XIV. A difference between the two line solution afforded 0.4 g. of solid acid which, after two compounds would be expected since the dimethy- crystallizations from methanol, afforded one of the stere;lene bridge forces XI into a more rigid configura- isomeric forms of 111 as colorless cubes, m.p. 192-193 . tion." A certain loss in fine structure is also ob- I t s ultraviolet absorption spectrum (A,,,, 265 mp, log e served in the spectrum of XI, particularly in the 2.45) was very similar to t h a t of 0-methyltetralin .lis Calcd. for ClaIIs,Ol: C, 70.41; 11, 8.82. l~c1111id: region between 230 and 274 mb where the parent C ,,4?td. i9.22; H, 8.98. hydrocarbon XIV has three distinct bands. The The cyclization of 50 ing. of the partially reduced acid same effect has been observed12 in this region in 111 with 5 ml. of anhydrous hydrogen fluoride at 0" yielded 1-methylbenzo [clphenanthrene (5-1nethy1-3,4-benz- 30 mg. of 6-keto-1,2 ,3,4,4a,5,6,9,10,11,12,I3a-dodecahyphenanthrene, XV) and may be attributed t o the drobenzo[c]phenanthrene (IV) which crystallized frorii molecular o ~ e r c r o w d i n g 'that ~ exists when groups methanol as stout cubes, 1n.p. 120-121'. Calcd. for ClsH..O: C, 85.04; IT, 8.M. Fouiitl: are located in the I-position of benzo[c]phen- C,Anal. 84.73; H, 8.47. arithrene (XIV). On the other hand, the dimethylThe 2,4-dinitrophenylhydrazone crystallized frciin lienene bridge also exhibits a fine structure effect, zene-methanol as red plates, m.p. 262-263'. observable in the 342- 399 mp region, aiialogous to Anal. Calcd. for C2rH2~Sa04: Ii, 12.00. Found: N , that reported for 4,lO-dimethylene-l ,%benzmthra- 13.25. cene.I4 cis- and truns-2-~-Naphthylcyclohexaneacetic Acids ( V ) .of 3 g. of lactone 11, 15 g. of amalgamated zinc, Acknowledgments.-The senior author (D.D.P.) A10mixture nil. of toluene, 20 ml. of concd. hydrochloric acid and 10 is grateful to the Alfred P. Sloan Foundation for i d . of water was refluxed gently for 72 hr. with the addition their support during the period 1935-193s. D.N. of 5 g. of amalgamated zinc and 10 ml. of concd. hydroC. wishes to thank the Damon Iiunyon Menlorial chloric acid every 12 hr. T h e reaction mixture was dilutetl water and extracted with ether. The ether solutioii Cancer Research Fund for a post-doctoral Fellow- with was washed with water and the acidic matter was extracted ship. with 5Yc sodium carbonate solution. rlcidification of the alkaline solution afforded 2.7 g. (90570) of an acid mixture E~perimental'~ which slowly solidified. I t crystallized from benzene -hex2-a-Naphthyl-2-hydroxycyclohexaneaceticAcid Lactone ane as colorless needles, m.p. 125-130". (II).-A Grignard reagent from 2.4 g. (0.1 g. atom) of magRepeated crystallization of this mixture from inetlianol or nesium, 20.i g. (0.1 mole) of a-bromonaphthalene in a mixhexane resulted in large losses without appreciable separature of 80 ml. of ether and 20 nil. of benzene was added with tion of the isomers. However, the separation was achieved stirring, at O " , to 18.4 g. (0.1 mole) of ethyl cyc1ohexa;ioneby taking advantage of the low water-solubility of the so2-acetatel6 in 100 nil. of dry ether. .After 2 hr. a t 0 and dium salt of tlie Lrans-acid. The acidic mixture was dissolved in hot sodium carbonate solution and tlie sodium salt (11) K . K,J o n e s , T H ~ sJ O U R N A L , 67,2127 (1Q45). It ishighlysignifit h a t separated on cooling w:is crystallized from water. cant t h a t the same effect is observed in the spectrum of the next higher Acidification of an aqueous suspensiorl of this precipitate I homolog. G,7-trimethylenebenzo [clphenanthrene, and t h a t the "u/B" salt afforded a solid acid that crystallized from aqueous ratio is the same (1.33) for both hydrocarbons (E. Clar and D. G. methanol to give 1.6 g . (53Yc) of trans-2-a-naphthylcycloStewart, ibid., 74, 6235 (1952)). hexaneacetic acid ( V ) us long colorless needles, m . p . 150(12) G. hl. Badger and I. S. Walker, J . C h e w SOL.,3238 (1964). 132". The analytical sample cr:;stallizcd from mcthnnol (13) F. €I. fierbstein and G. M. J. Schmidt, i b i d . , 3302 (1964); as iieedles, 1n.p. 158-1GO". Its ultraviolet absor1)tiri~l hI. S. Newman and W. B. Wheatley, THISJ O U R N A L , 70, 1913 (1948). (log e ) 225 1np (4.941, 273 (3.811, 282 spectrum (Ams,. (14) W. Dirschel and F. Hanusch, 2. p h y s i o l . Chem., 233, 13 (1935); (3.90) and 313 (2.05)) \I s very similar t o that [ i f n-meth>-lK. N.Jones, Chem. Reos.. 32, 29 (1543). naphthalene.'7b (15) Llelting points and boiling points are both uncorrected. Infra..lnnl. Calcd. for ClaESy,O~:C , SO.60; 11, 7.40. Fouiicl: red absorptivn spectra were meawred on a Perkin-Elmer model C, 80.95; H , 7.32. 21 R spectrophotometer, Ultraviolet absorption spectra were meas\,
ured with a Beckman model D K automatic recording spectrophotometer in 95% alcohol as solvent. Analyses are by Schwarzkupf Labs., ' . Woodside 77, N . 1 hla. Ber., 68, 871 (1'335).
( l i ) R. A. Friedel and M. Orchin. "Ultraviolet Spectra of Aromatic Hydrocarbons," John Wiley and Sons, Iiir , N e w York, N . Y . , 1931, (0) c h a r t no. 11, (b) chart nu. 196
Aug 20, 1938
SYNTHESIS OF 6 , i - A C E B E N Z O [C ]PHENANTHRENE
436i
[clphenanthrylideneacetic acid (VI, R = H) which crysThe mother liquor that remained after separation of the insoluble sodium salt was acidified t o give 1 g. of semi-solid tallized from absolute ethanol as colorless plates, m.p. 242" (log E): 221 mp (4.32), 265 acid which was dissolved in benzene. T h e solution slowly dec. T h e ultraviolet (A, (4.55) and 310 mp (4.29)) and infrared (A, 5.93 p ) abdeposited 0.2 g. of the cis-acid as colorless plates, m.p. 190195". Two crystallizations from benzenemethanol af- sorption spectra were in agreement with its formulation as forded pure cis-2-cu-naphthylcyclo)exaneacetic acid (cis-V) an a,p-unsaturated acid. as colorless plates, m.p. 219-220 . I t s ultraviolet absorpAnal. Calcd. for C~0H2002:C, 82.19; H , 6.80. Found: tion spectrum was essentially superimposable on that of the C, 82.23; H , 6.73. trans isomer. 1,2,3,4,4a,5,6,13a-Octahydrobenzo [c]phenanthrene-6Anal. Calcd. for ClsH2002: C, 80.60; H , 7.46. Found: acetic Acid (VI1).-.4 solution of 1.28 g. of the unsaturated C , 80.13; H, 7.40. ester VI, (R = C2H5),m.p. 125-126", in 25 ml. of absolute T h e benzene mother liquors, after separation of the cis- ethanol was reduced at atmospheric pressure in the presence acid, m.p. 190-195', were diluted with hexane. The solu- of 0.2 g. of 10% palladium-on-charcoal catalyst. The absorption of hydrogen was very rapid and about 90% of the tion slowly deposited 0.5 g. of colorless needles, m.p. 130theoretical amount was taken up in 1 hr. 135", evidently a mixture of the isomeric acids V. After 3 hr. at room temperature, the solution was filtered trans-6-Keto-l,2,3,4,4a,5 ,6,13a-octahydrobenzo [c]phenanthrene (I).-To 30 ml. of anhydrous hydrogen fluoride and the viscous oil that remained after removal of the solcontained in a polyethylene bottle and immersed in an ice- vent was saponified by heating with methanolic potassium bath wa: added 2.01 g. (0.0075 mole) of trans-acid V, m.p. hydroxide. Removal of the alcohol under reduced pressure 150-152 . The dark red solution was kept a t 0" for 10 followed by dilution with water and acidification of the min. and then was poured onto 200 g. of crushed ice. T h e alkaline solution afforded 0.95 g. (817') of colorless granules which were dissolved in benzene. The solution slowly deorganic material was extracted with ether and the ether posited 0.3 g. (267,) of acid, m.p. 205-208'. Recrystallizasolution was washed several times with water and then with sodium carbonate solution. Removal of the solvent tion from methanol afforded one of the stereoisomeric forms 1,2,3,4,4a,5,6,13a-octahydrobenzo[c]phenathrene-6left 1.85 g. (98%) of solid ketonic material which was dis- of solved in benzene. After the removal of 0.3 g. of a ketonic acetic acid (VII) as colorless needles, m.p. 216-217'; Xmnx (log E): 232 mp (4.87), 283 (3.68), and 323 (2.46); 5.86 p . by-product of unknown structure, the mother liquor was concentrated and diluted with hexane. T h e solution Anal. Calcd. for C20H2202: C, 81.63; H , 7.49. Found: slowly deposited 1.45 g. of impure I , m.p. 140-145O. C, 81.45; H , 7.53. Vacuum sublimation followed by crystallization from benT h e benzene filtrate from the separation of the acid, m.p. zene-methanol afforded 1.12 g. (60%) of druns-6-keto- 205-20S0, was diluted with hexane. The solution deposited 1,2,3,4,4a,5,6,13a-octahydrobenzo [clphenanthrene (I) as 0.5 g. (43%) of stout prisms, m.p. 159-160". rectangular plates, m.p. 154-155", A,, 5.95 p . T h e m.p. Anal. Calcd. for CsoH2202: C, 81.63; H , 7.49. Found: was undepressed on admixture with the ketone obtained from the reaction between trans-2-hydroxycyclohexaneace- C, 82.05; H, 7.54. In view of the subsequent experiments with this material, tic acid lactone and naphthalene. it appears t o be a mixture of the stereoisonieric forms of The 2,4-dinitrophenylhydrazone crystallized from benzene as red needles, m.p. 272-273", lit.6 m.p. 186-188" (see VII, although the m.p. was unchanged on repeated crystallization, Discussion). l-Keto-4,5-tetramethylene-6,7-benzo-Za,3,4,5-tetrahyfrans-l,2,3,4,4a,5,6,13a-Octahydrobenzo [c]phenanthrene. droacenaphthene (VIII).-The cyclization of 0.25 g. of the -Fifty milligrams of ketone I was refluxed gently for 2 hr. with 1 ml. of hydrazine hydrate solution and 5 ml. of ethpl- acid VII, m.p. 205-208", was accomplished by treating with 10 ml. of anhydrous hydrogen fluoride a t 0". After 10 ene glycol. To the cooled reaction mixture was added 0.5 g. of solid potassium hydroxide and the solution was slowly min. at ice temperature the dark red solution was poured onto 100 g. of crushed ice. The usual workup gave 0.24 g. heated to a bath temperature of 220" a t which it was maintained for 4 hr. The usual workup followed by chroma- of neutral material which was taken up in benzene and tography on alumina afforded 40 mg. (85%) of the hydro- passed through an alumina column. Concentration of the carbon which crystallized from methanol in colorless silky benzene eluents afforded 0.21 g. ( Q O ~ c )of one of the isomeric forms of l-keto-4,5-tetramethylene-6,7-benzo-2a,3,4,5-tetraneedles, m.p. 109-110°, lit.6 m.p. 47' (see Discussion). hyd:oacenaphthene (VIII) as colorless needles, m .p. 160Anal. Calcd. for ClsH20: C, 91.52; H , 8.48. Found: 162 . Recrystallization from benzenemethanol afforded C, 91.34; H , 8.72. an analytical sample, m.p. 164-168". I t showed the characT h e dehydrogenation of 20 mg. of this hydrocarbon by teristic infrared absorption of a conjugated 5-membered ring heating for 1 hr. a t 300-320" with 10 mg. of 10% palladiumketone a t 5.85 U . The ultraviolet absorDtion suectruni on-charcoal catalyst gave 10 mg. of benzo [clphenanthrene showed A,, (log'€): 218 mp (4.37), 252 (4.?3), 297 (3.91), (XIV), m.p. 65-66', identified by mixed m.p. comparison 308 (3.97) and 355 (3.44). with an authentic sample. Anal. Calcd. for C20H200: C, 86.95; H , 7.24. Found: Ethyl trans-l,2,3,4,4a,5,6,13a-Octahydro-6-benzo [c] C, 86.73; H,7.07. phenanthrylidene Acetate (VI, R = C2H5).-A mixture of 1.25 g. (0.005 mole) of ketone I , 25 ml. of dry benzene, 25 The 2,4-dinitrophenylhydrazone crystallized from benml. of dry ether, 0.6 g. of 20 mesh zinc, 1 ml. of ethyl zene as red plates, m.p. 255-256' dec. bromoacetate and a crystal of iodine was heated under reflux Anal. Calcd. for C ~ B H ~ ~ O C,~ 68.42; N ~ : H, 5.26; N, with stirring for 8 hr. After one hour a pale yellow complex separated from solution and after 4 hr. 0.5 g. of zinc and 9.5 12.28. Found: C,68.40; H, 5.51; N, 12.41. inl. of ethyl bromoacetate were added. The cyclization of 0.7 g. of acid VII, m.p. 159-160", with 10 ml. of anhydrous hydrogen fluoride as described above The reaction mixture was hydrolyzed by dilute hydrogave 0.5 g. (75%) of a mixture of the isomeric ketones VI11 chloric acid and the organic layer was washed with water and dried over sodium sulfate. Removal of the solvent left a as colorless needles, m.p. 125-130". Recrystallization of viscous oil which was dehydrated by heating for 10 min. this material from hexane and finally from methanol afforded with 5 ml. of anhydrous formic acid. T h e semi-solid mass 0.15 g. of the other isomer of VI11 as soft needles, m.p. 165after removal of the formic acid was dissolved in benzene 166'. The mixed m.p. with the 164-165' isomer (see and passed through an alumina column. Concentration above) was 140-145'. An analytical sample obtained by of the benzene eluents afforded 1.55 g. (97%) of the unvacuum sublimation followed by crystallization from saturated ester VI ( R = C2Hs) as colorless needles, m.p. methanol had m.p. 168-169", Amax 5.85 p . 125-126'. Recrystallization from benzene-hexane proAnal. Calcd. for C ~ O H ~ OC, O :86.95; H , 7.24. Found: vided an analytical sample as soft, silky needles, m.p. 128'. C,87.35; H, 7.47. (log E): 221 mp Its ultraviolet absorption spectrum (A, The 2,4-dmitrophenylhydrazonecrystallized from pyri(4.33), 274 (4.52) and 312 (4.30)) was in agreement with dine as red plates, m.p. 270-271'. the assigned structure. Anal. Calcd. for N, 12.28. Found: N, Anal. Calcd. for C Z ~ H ~ C, ~ O82.50; ~: H, 7.50. Found: 12.03. C, 82.39; H, 7.48. The combined mother liquors, after separation of the Saponification of a part of the material afforded a quantitative yield of trans-l,2,3,4,4a,5,6,13a-octahydro-6-benzo- 165-166" isomer of VIII, were concentrated to give 0.3 g. %
-
of solid, rn.1). 1SX-.1:(233, e\~itlentlya mixture of the two stercoisomers (VI11). 1.2,3,4,4a,5,6,13a-Octahydro-6,7-acebenzo [clphenanthrene (IX).-.l mixture of 0.11 g . tJf ketone VIII, n1.p. l64--165', 1 nil. of 8 5 5 hydrazine hytlrate and 5 nil. of ethylene glycol was refluxed gently for :la s r7iicrocr).stailiiie iicetllrs with L: faint yellow cast, i n . p . 115--11s". F \ c q ) t
for :t small amount of fluorescent tarry material, no other products could be eluted with benzene. For purification, the hydrocarbon XI was converted to the. 2,4.7-trinitrofluorenonecomplex, reddish needles from benzeiic-methano!, 111.p. 192-193'. T h e analysis iudicated that the ratio in this complex was not a simple one but agreed with a rntin of 1.33 : 1 for XI and the reagent, . ~ ? Z ( L ~ . Calcd. for 4/3(C2oH11),ClsH6S307: C, 72.7S; 11, :3.65. Found: C, T2.12; H , 3.79. 'The hydrocarbon 9 1 \vas regenerated from the trinitrofluorenone complex by passing a benzene solution through mi alumina column arid crystallized from methanol as colorless needles, m.p. 125-12G'. . I d . Calcd. for Cl0III4: C . :)1.48;II, 5.52. Found: C, 94.35; H, 5.70. The sym-trinitrobenzene complex cryst,illized From l w i zeiie-methanol as red needles, m . p . 181-185". .lnnl. Calcd. for CZ6HI7K3O6:C 66 81; I I , 3.64. Found: C, 66.56; H , 3.83. The ultraviolet absorption spectrum of the hydrocarboil S I (Fig. 1) showed the following maxima (log e in parentheses): 230 mp (4.18), 274 (4.63), 284 (4.79), 295 (4.10), 302 (4.03), 316 (3.97), 32'7 (3.58), 342 (3.101, 359 (3.3'7), 378 (3.48) aiid 399 (2.90). The yield of hydrocarbon X I could not be improved by changing the reaction conditions. Essentially no product could be isolated by dehydrogenation of I X at higher teni~)eraturesfor a shorter period or at lower temperatures for a longer period of time. Similar results were obtained from the dehydrogenation of the mixture of hydrocarbons I X obtained from ketone I without extensive purification of intermediates although the yields of XI were somewhat lower. >foreover, from the later fractions on the chromatogram there was isolated a srnnll amount (2:;) of 3,4-benzpyrene (XIII), m.p. 170-172', identified by mixed m . p . with a n authentic specimen. -111 attempt was made to prepare the hydrocarbon XI from the corresponding alcohol X by the method successfully employed in the synthesis of cholanthrene.1s Lithium aluminutn hydride reduction of V I I I , m.p. 166-165', afforded a 6055 yield of l-hydroxy-6,7-benzo-4,5-tetramethylene-Za,3,4,5-tetrahydroacenaphthene ( X ) as silky needlcs from hexane, m.p. 160-161'. .?rial. Calcd. for CznHsnO:C, 86.33; H , 7.iIl. Fountl: C, 85.95; H , 7.74. The alcohol was dehydrated by sublimation at 0.1 nim. and the sublimate was dehydrogenated by heating for 1 hr. to 300-;310" with loc$ palladium-on-charcoal catalyst. Complete destruction of the molecule occurred, however, and no hydrocarbons could be isolated from the re:ictioii. .
~~
(18) \V, E. H a c h m s n n :in
