304
FAHRENHOLTZ, CAPOMAGGI, LURIE,GOLDBERG, ASI) Iolved i i i 250 ml of meth:tiiol, mixed Tvith 100 nil of I..? .\- TICI, and allon.ed to > t : i i i ( l at room temperatiire overnight . The mixtiire \v:is diliir rtl with water arid extrac,ted Lvith dichloromethane, ailti the orgaiiic. extracts were extraded with 1 .V S a O I I . The basic. extract3 \ T - ~ w acidified and extracted with tlic.hloroiiieth:tlie. lulf:tte. The reactioti mixture I T X L stirred a t t h e t i filtered t o give 1S6 riig ilc, nip 156-l5So, uiidepre~he ple of XI% prepared froni tlip BBIC-trans dimethcisy
C', 6 7 3 1 ; 11, 7 . 0 5 , Preoaration of 2o1-AlkvI-1.4.4a~.9.lO.lOa~-hexahvdro-6.7-di. metho:~y-3(2H)-phenanthrenones (XVIIIe-g j. General Method C.-- The (.rude SVIIb (geiieral method A ) froiii 0.0:3 iiiole of I
,
SVIb w:i> tiiiscd wit11 40 1111 of water, 80 nil of riietJiaiicrl, : t i i t 1 0.075 iiiole of IGCi id, and the resulting solution was heated itiitler refliix overnight. The woled reaction mixture was diluted witti \\-:iter a i i d extractccl with dichloromethane. The extracts ~ v w e dried (,?;a?SOa) iiiid coriceritrated under vncuunii to give a residiic. from \\hic.li S\TIIc--g could be cryatallized (see Table I). Z~-EthyI-l,4,4a~,9,10,10ap-hexahydro-6,7-~imethoxy-3(2~ )phenanthrenone (XVIIIe). From XII1b.-A solutiou of 300 nig (1.05 riiinole.) of SIIIb, 100 mil of benzetie, and 5 1111 of cthyleiie glycol roiitiiitiiiig 25 irig of p-toluene~:ulfoiii(:acid xv:i~ Iie:tt,ed 1,4,4aa,9,10,10ap-Hexahydro-6-methoxy-3~2H)-phenanthre- iuider refliix ( I )enti -Stark trap) overnight. The c*croledre none (iiij.-To a stirred suspeiwioii of 625 riig (0.0024 mole) of i ~v:i> then poured iiit,o water containing : i ~ i esc iii 8.0 rill of CCl, mi added enough tetrahydrofur:tii to affect :iii(l w i - cLsfracd (CHgCI,). The extrada were dried coniplet e ~olutioii:it room temperature (15.6 nil), 0.335 nil o f ) i ) :iiitl coiic,eiitrated to :iii oil. The latter mixture, (lisdiethyl phosphite,Z3 aiid 0.38 nil of triethylamiiie. After stmidiiig -;olved i n .i n i l of 1(?tr;ili?.dr'tifiiraii, w:is added over 1U i i i i i i t~ LI :it room temperatiire for 4 days, the reac~tioiimixtiire \vas diliited stirred arid refluxing solutioii of 1.0 g ( 2 5 ing-atoilis) of potassiuiii with chloroform, waqhed w i t h lvaier theii Lvith diliite IICI, iii 20 nil of licliiid :mitiiiriii:L idistilled through :L t o v x r filled rvitli :tiid t heii extracted with diliite NaOFf. Acidification of the KOH pellets). TIP rtiisture was stirred for :LII :xlditiorial 30 babic: e s t r x t s gave 224 nig of recovered btmtiiig materia!. r i i i i i whereiilviii aii esces:- of KH4C1 vas added t o diachnrgc the 'l'tie original chloroform soliitioti \vas dried (Xa2S0,) and COIIhliie color. T!te :iniiii~itii:i wts allowed t o evapornte, :tiid t lie c~mtratedto a colorles,~oil. The latter material wi~: dissolved i t i i,esitiiit~w:i. 1ii1iiie.d \vi1 11 witer :tiid extrarted with ~ I i ~ ~ l i I ~ ~ ~ ~ i r i ~ ~ ~ ~ l : j . O nil of tetrahydrofriraii a i d the resiiltitig solution \vas vooletl :iiif', Tlie cxtr:ic.t 'I \vilre dried :tiid conceiitr;ttetl to :iii oil, ivliicli i i i a 1)ry Ice bath. Liqiiid ammonia [ 10 nil) (dist,illedover KO11 \vas diisolveti i i i 10 nd of riicthnriol aud mixed ~ v i t h2 nil of :) .\' pellets) \ v w added, aiid the ~ ~ l i i t i o wtts t i allowed to warm to I~IC1. T h o rwiiltiii oliition \vas allowed to >t:ttid at, roiriii reflux temperatiire. T o this Inistiire i w s added 76 nig (3.:E temperntilie fiir :: ( aiid theii diluted with 10 nil of \vatw. mg--atonis) of aodiiini, which gave a monieiitary Miie c ~ j l o r Tlir resitltiiig pi'ec.ipit:ite \ ~ a scollected :znd recrystallized t n i w follo~vedliy the appearance of :i yellon- precipitate. ;iflei- thc lroiii rrielhuiiol to give 4 mg of S \ T I I e ~nil) 144-145', a~itici,e:i(atioii niixt,iire had >tirred for i i i i ntlditioiial 1 0 n i i i i :it refliis pres-ed i i p i i i :iclmisiiu'e wit11 :L satnjile of X\'IIIe prcparetl f r o n i ternperntiiro, 3 rill of ethaiiol nxs d d e d . Tlie amnioiii:~iva.. S\?b. a1lon.d to evnpor:tte cind the residiir, after diliitioii with benzene, \\:is \v:i-hed with diliite HCI, m t e r , diliite S>tOII, arid finally with water. The organic. layer \ \ a s dried (SanSOd) aiid coiiAcknowledgment.-\e arc, iiidehted t o 1)I*. .I1 rated t o it c,olorles.~oil wliic~h after crystallizatioii aiid reSteyermark arid his \taff for the iiiicroanalyie\, atid l o .tallizatio~ifrom methanol gave 55 nig (1*5(i ) of the aiialyticd TI?. T. Toomu, DT. E. Billeter, and A\Ir,S. Trairiiaii f o r -:,5 ( i n f l ) mp ( e 6000), ?SI '17 pie of j j i : mp < J T . ~ - Y ~ " ;x"!'n ,",',"j (21iO)j arid 280 (19eO); Y ~ , , ' ~ ~ ' ' , "I "T 1 0 th(. ultraviolet, iiinr, arid infrared sped ra, respec.tj,cly. for C1511is02:C, 7 r J s 7 . ~ 8 . Folllld: c:, \Ve are also indebted to Dr. -1.Brossi for his iiitercst 1
6,7-Dimethoxy-1,4,4acu,9,10,10ap-hexahydro-3( 2H)-phenanthrenone (XVb).-A d u t i o t i of 41 .?Ig (0.136 iiiole) of XIVb iii 1 1. o f niethniiol w a mixed ~ with 200 nil of 3 S HCI. After staiidiiig
arid eiicouragenieiit during this work. It is a pleasurv t o acknowledge the tcdiiiical assistance of 1Ir. .J. ( i. A\\lulliiiand 11r. T. IT.IGmiedy.
