S>tithetic BradSkinin h a l o g s
Experimental Section"
14a,l7~-Ethenopregn-5-en-3p-ol-20-one Acetate (IId).--4
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Iutioit of 6.0 g of I in it?nil of benzeiie \vas heated a t 160" ~indcrethylene at 3000 atm for 14 h r . Then the mixture was woled, filtered, arid evaporated to dryiierc. under reduced press-~~r('. Tlie re>idiie was taken iri met,hanol and filtered to i w i o v e the insoluble polyethylene. 'The residue, obtained by ilistilling the filtrate, was chromatographed over 125 g of acid-
washed alumina. (hexane-benzene). Crystallization from meth:in01 gave IId, iii a yield of 3.44 g ( 5 3 ) na white rods: mp 140-142°; vsuJ''l 1730>1701 c111-1. The nyl protons appeared iii the rinir spec.triini :Lt 6 5.45 ( i n ) , 6.05 ((1, ,T = 6 cps), and 6.16 ((1, J = 6 c p ) . -4naE. Cialcd for CzjH&: 7S.49; 11, 8.96. F o u n d : C,!, 7 8 . 3 ; €I, 9.12. 14a,l7a-Ethenopregn-5-en-3~-ol-20-one (Hej.-- -After a misiiirc of 1.41 g of 113, 1.46 g of KOFT, 6 ml of water, and 50 ml uf cthaiiol had been stirred a t room temperature for 20 hr, it, wac: c,oirctntrated undcr v a ~ u u i naiid theii partitioned between erher : t i i d water. The ether extract was dried (MgSOI) and theti c~aporai,edto dryness urider reduced pressure. Crystallizat,ioii from etlictiiol afforded IIe, i n a yield of 1.12 g (Si%), as white ~icctlles: nip 196-198"; v ~ ' ' ' 3636, ~ ~ 1675 cm-l. The nmr i p w t r u m showed a singlet n t 6 3.18 (21-CH3)arid peaks at, 5.4'7, 0.03, : i i i t l 6.17 iwrespoiidiiig to the (i, 15, and 16 protons, rehpectivt4~-. *Inul. C:al(d for C:ynEf,&: (:, sI.13: 11: 9.47. E'niiiid: C, so.91; 11, 0,:Hj. 14~,17~Ethenopregn-4-ene-3,2O-dione(IlI).----h niixturt. ol - 2 g of Ile, !I,.> nil of cyclohexa~ione,and 180 ml of tvlueiie w a s o t r i J p t d iiiidrr D Ileart--Stark htvtd ffJr 1.5 hr. Then, 1.68 g iliiniiltiiiri i.~i~irop)xide was nddetl a i d reflus cont,inued for J.,? hi.. A f r t x the m n t i l t i i i g solriticiii had been cooled to mom tcinlw:itiirt', ii wa? a-nihetl nit11 :qiieoiis HClj dried (AlgSOaj, :riiiI v o i i i w i t r n t c d iiiiiier rediicd pressure. The residiie w:ts I ~ ~ i r ( J I ~ i : i ~ ~ ) over g ~ ~ l45 p l ige of ~ ~\\'oelni iieutral :tlirniina, a,etivit>g x ( l v I. :Ift er inipiirit i e i had IJeell elatrd by be~izeiie-h~s:me
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