990
VOL.
KOTES
(0.7 mole) of finely powdered ammonium carbonate monohydrate and 400 ml. of acetone. From a dropping funnel, 126 g. (0.5 mole) of diphenyldichlorosilane dissolved in 150 ml. of aret,one was added portionwise into thc flask, which was .shaken gently during the addition. By the addition, ammonium chloridc precipitated as fine vhite crystals and carbon dioxide was evolved readily; the gas evolved from the reaction mixture immediately precipitated barium carbonate when it was led into barium hydroxide aqueous solution. After the addition was complete, the contents were refluxed gently for about 1 hr. The product. was filtered by suction after cooling and the colorless filtrate was then evaporat.ed t o dryness on a wat,er bath; a white rieedle crystalline mass melting a t 122-126" was obtained. Further purification was effected by recrystallization from purified methylacetate; 100 g. (93%) of white needles were obtained. Bnnl. Calcd. for C12E112SiOZ: C, 66.62; H, 5.59; Si, 12.97: mol. wt., 216; OH/moleciilc, 2.00. Found: C, 66.3; H, 5.20; Si, 12.8; mol. u t , 190-198 (glacial acetic acid); OH/ molecule, 1.97 ( I h r l Fischcr titration*). Density of a single crystal wht.11 measured in calcium chloride aqueous solution of matched density was 1.16 (at 25'). The infrared absorption data were in complete agreement with those given by Tatlock arid Rochow.9 Regarding the melting point of this diol, t.he wcll known abnormality was confirmed: For example, needles obtained from acetone ether melted ut 155", needles from methylacetate melted a t 147-148'; moreover, somc needles which melted a t 131-133', 142-144', 158-160" were also found diiririg many measurcmcnts. Melting was always accompanied by formation of liquid decomposition products itnd the measurement of melting point was always carried out using clean Pyrex capillary tribe arid a t t,he rate of heating 5' per min., the bath being preheated a t about 110'. Further invcstigntions on the possiblc existence of polyor mesomorphism of this diol are being iindcrtakcn by using x-ray technique. C!/clodiphenylsiloxanes. ( A ) Tri7ner. The crude crystalline mass obtained in the procedurc described above was dissolved in 1000 ml. of ether, and 30 ml. of concentrated hydrochloric acid was addcd. The mixture was gently refluxed or about 2 hr. and then evaporated to dryness on a water bath. Recrystallization from cthanol benzene gave 75 g. (777,) of hexaphenylcyclotrisiloxane melting a t 189". (B) Tetramer. The filtrate obtained i n the above procedure was concentrated in the presence of a small grain of sodium hydroxide. White cryst,als precipitated upon cooling; recrystallization from ethylacetate gave 81 g. (82%) of octaphenylcyclotetrasiloxane melting at, 201'. These cyclodiphenylsiloxanes were well identified by their x-ray powder pattern data.10
Acknowledgment. The author thanks the Shinetsu Chemical Industrial Co. for supply of pure diphenyldichlorosilcne. DEPARTMENT OF APPLIEr) CHEhIIsTRY KIRYUCOLLEGE OF TECHNOLOGY GUNMA UNIVERSITY, KIRYV,JAPAN
(8) H. Gilman and 1,. S. hlillcr, J . Ana. Chena. Soc., 73, 2367 (1951). (9) W. S. Tatlock and E. G. Ilochow, J . O q . Chem., 17, 1555 (1952). (10) J. F. Hyde, L. I(.Frevel, H. S. Xutting, P. 8. Pctric, and 51. A. I'urcell, J . :lm. Chrni. Soc., 69, 488 (1947).
24
Steroidal Hormone Relatives. VI. The Condensation of Cyclopentanone with 1-Acetylcyclohexenel J. H. BURCKHALTER AND P. K U R A T H ~ Received November
e.4, 1968
This report describes part of a continuing program in the synthesis of model compounds which contain a carbonyl group in a position corresponding to the 11-keto of c o r t i ~ o n e .I~n the present approach, 1-acetylcyclohexene was condensed with cyclopentnnone under dknline conditions in an effort to obtain a Michael reaction product which mould then undergo an aldol type reaction to give 5-keto-A.""c4)-decahydro-l-benz[elindene (I). 4 Compound I would offer a possibility for bromination
0
)
I
$o I1 n
I11
IV
in the allylic positions corresponding to C-17 of the steroids and thus open a route to the dihydroxyacetone side chain of cortisone. Various attempts to obtain I by the condensation of 1-acetylcyclohexene and cyclopentanorie in the presence of sodamide in lithium amide in ether,4b sodium in an excess of c y c l o p e n t a n ~ n e , ~ ~ and potassium isopropoxide in pyridine,4d yielded instead of I a mixture of 3-cyclopentylidene-&ketoA3a(4)-decahydro-l-benz[elindene (11) and 2,5dicycloperitylidenecyclopentanone (111). It has been pointed out by Wallach that cyclopentanone condenses with itself in the presence of sodium ethoxide to form I11 and 2-cyclopentylidenecyclopeiitanone (IV).S It appears that under the conditions employed to prepare the alkali metal ______
(1) Aidcd by the General Research Fund, Univrrsity of Kansas. ( 2 ) Abbott Laboratorips, Sorth Chicago, Ill. (3) J. IS. Biirclthalter :m(i P. Kurath, J . ' t m . Cheni. Soc.. 81,895(1959). (4) Earlier npproachcs in this direction may be scen in the studies of Robinson and others: (a) 1%'. S. Rapbon and It. Robinson, J . Chem. SOC.,1285 (1935); (b) A. J. Birch and It. Robinson, J . Chem. Soc., 503 (1934); (c) C. A. Friedmann and R. Robinson, Chem. and Znd. (London), 777 (1951); and (d) W. Huber, Ber., 71, 725 (1938). (5) C. Djerassi, Chem. Revs., 43,271 (1948). ( 6 ) (a) 0. Wallach, Ber., 29, 2955 (1896); (b) R. hIayer, Rm.. 89, 1413 (1956).
derivative of cyclopentanone, the latter under- crude 11, b.p. 155-184' (0.3 mm.). After several rerryswent self-condensation to form I11 and IV. The tallizations from acetone, it melted at 167-169" and the melting point was not depressed by samples obtained earlier 2-cyclopentylidenecyclopentanolle (IV) then re- (vzde supra).":::A( 308 mp, c 1.42 X IO6; 250 mp, acted with 1-acetylcyclohexerie to give 11. A s a e4.03 X lo4.) Anal. Calcd. for CIRHZdO:C, 84.32; H, 9.44. Found: C, confirmtLtion of structure, I\' was prepared6 and treated with I-acetylcyclohexene in the presence of 84.52; H, 9.54. The 2,4dznztrophenylhydra~o7ie of I I was prepared and sodamide b y analog with earlier work4 to form I1 recrystallized from chloroform as a rcd crystalline solid, in 40% yield. A 2,4-dinitrophenylhydrazone of I1 m.p. 243-245' dec. was prepared. Also, the absorption maximum of I1 Anal. Calcd. for @24H28N404: C, 613.03; H, G.47. Found: in the ultraviolet was found to be at 308 mp; ii C,65.87; H, 6.52. value of 316 was calculated by the rule of WoodLABORATORY OF PHARYACEUTIC.iL CNEhiISTRY ward for conjugated dienones.7 1;NIVERSITY O F KANSAS LAWREKCE, KAN. Compound I1 is a substituted a-decnlone prepared under alkaline conditions where only the trans- forin has been considercd to be Thus, I1 may have trans- ring fusion between the Steroidal Hormone Relatives. VII. Allylic rings corresponding to rings 13 and C in the steroid Bromination of trans-9-Keto- A",-decahydroseries where the same stereocheniical arrangement phenanthrene1 was est,ahlished. I-Iowever, since no proof is uvailable, it is preferred to leave the question open. J. H. BURCKHALTER AXD P. K U R A T H ~ EXPERIMENTAL
Received iVovember 34, 1968
Attewipled sqnthesis of 6-kelo-A3a~"'decuhydro-l-benz[e]indene (I). Cyclopentanone and I-acet~ylcyclohexene~in A further search for a cyclic a,p-unsaturated 0.08 molar amounts were used under conditions suggested by ketone as a model compound which would offer the work of Birch and Itobimo11.~~~ Distillation of the ether soluble material gave 5 g. of a pcllow oil which distilled a t a possibility for bromination in the allylic position 75-150' (0.3 mm.). Itedistillution gave 2 g. of oil of b.p. corresponding to C-17 of the steroids3 resulted in 125" (0.3 mm.) which solidified, n1.y. 82-84". After several the selection of trans-9-keto-A'O-dodecahydrophenrecrystallizations from met.hyl alcohol the yellow 8,6- nnthrene (I).4 dicyclopat~~lzdeneeyclopelltnnone(111) melted a t 89-90'. Admixture of this compound with I11 of' t,he same melting 0 point, obtained from cyclopentanone in the presence of sodium ethoxidee, did not depress the melting point [lit., b.p. 190' (12 nim.)h; m.p. 7 6 - 7 7 O 6 y b.p. 198-200' (12 mm.)eb; m.p. 81.5-82°6b]. The substance would not readily form a O p ketonic derivat,ive, and, after a few dags, it darkened badly. .4nal. Calcd. for ClsH&: C, M.28; H, 9.32. Found: C, 83.02; H, 9.35. Reaction of I with N-bromosuccinimide in the Continued distillation at, 150-170" (0.3 mm.) gave 1 g. absence of ultraviolet irradiation, according to the of highly viscous, oily 3-cyclope~ilylidene-6-keto-A~~~~~decahydro-l-buir/lt[e]indene (IT) which crystallized upon treat- experimental procedure of Meystre and Wettment with acetone, n1.p. 161-164'. After several recrystal- stein,6followed by treatment of the crude brominalizations from acetone, the n-hite needlcs melted a t 167tion product with cuprous cyanide,6 yielded a 169". mixture from which no pure product was isolated. Anal. Calcd. for C1&40: C, 84.32; H,9.44. Found: C, However, since hydrogen bromide was formed dur84.48; 11,9.41. S-C~~rlopentylidene-5-ket0-A~~~~~-decaliydro-l-benz [ e ]indene ing the bromination step, it was dccidcd that bromi(11). To a suspension of 3 g. (0.077 mole) of sodamide i l l 180 nation had occurred and was followed by the inml. of dry ether in a nitrogen atmosphere, 11.6 g. (0.073 troduction into 1 of a second carbon-to-carbon mole) of 2-cyclopentylidenecyclopentanone (IV)fiwas added with stirring and cooling during a period of 15 min. Tha double bond. A repetition of the bromination experiment, mixture stood then for 6 hr. at room temperaturr ant1 was finally refluxed for 1 hr. With stirring and cooling 9.6 g. followed by a dehydrobromination procedure em(0.077 mole) of I-acetylcyclohexenc was added. After st,snding overnight, the mixture was treated with GO ml. of dilut,r ( I ) Aidcd by the 'Genrral Hcwarch Fund, University of sulfuric acid and then ext,racted with cthw. The extract was Kansas. handled in the usual manner t,o give, 7.0 g. (407%yield) of (2) Present address: Abhott Laboratories, Xorth Chicago, Ill. ( 7 ) I,. F. Fieser and M.Firser, A'nlural I'roducls Related (3) J. H. Burckhalter and P. Kurath, J. Org. Chem., 24, to Phenanthrene, 3rd ed., Reinhold Publishing Corp., New 990 (1959). York, K. Y.,1949, p. l(32. (4) W.S. Rapson and R. Robinson, J . Chem. SOC.,1285 (8)(a) W. Huckel, Ann., 441, l(1925); (b) R. P. E n - (1935); It. P.Linstoad, S. B. Davis, and R . R. Whetstone, stead, W. 13. Doering, s. B. Davis, 1'. L c v i n ~ ,and It. R. J . Am. Chem. Soc., 64, 2009 (1942). Whetstone, J . Am. Cheni 8or., 64, 1985 (1942); (c) It. 1'. (5) C. Meystre :md A. Wettstein, Experientia, 2, 408 Linstead, R. R. I)avis, and H . It. Whetstone, J . Am. Chem. (1946); C. Iljerassi, Chem. Revs., 43, 271 (1948). Soc., 64,2009 (1942). ( 8 ) J. V. Supniewsky and 1'. 1,. Sdzberg, Orq. Sptheses, (9) ,J.IT. Smndcrs, Orp. Synthews, Coll. Vol. 111, 23 (I!J55). coll. Vol. I , 46 (1941).
p
Hop
