ml of distillate was removed over 3 hr. Work-up afforded a residue which appeared to contain V but which gave 4 spots on tic and appeared to be far less pure by nmr than was the V prepared as in A.14a,17a-Etheno-16a-carbomethoxyandrost-4-en-17-ol-3-one Acetate (VI). -A mixture of 418 mg of crude V, 1 ml of methyl acrylate, and 5 mg of hydroquinone was sealed in a glass tube under reduced pressure, and then heated to 120°for 116 hr. The mixture was then evapd to dryness under reduced pressure. The residue was warmed in Me.CO containing 1 drop of aq HC1 for 10 min and then again taken to dryness. The residue was chromatographed over o() g of acid-washed alumina. Elution with CeHe-EtOAe mixtures afforded material which crystallized from Et.O-hexane to afford VI, in a yield of 160 mg (34',')) as white needles: mp 1.83-1.85°c; rN,|i"1 1745 Csh} 1730 (broad) and 1675 cm h The nmr had 3-IV" singlets at <5 1.00 (C-JS-Il's), 1.17 (C-l Sill's), 2.11 (acetate), and 3.65 (OMe), and a 1-11* multiplet at 5.8 and 1-H " doublets at 6.11 and 6.34 (./ = 6 Hz). Anal. iGMKOKC.IL 14a,17a-Etheno-16a-carbomethoxy-5«-androstan-17-ol-3-one Acetate (VII).-A solution of 100 mg of VI in 25 ml of MeOH was hydrogenated over 10 mg of 10' ( Pd -C at 3.6 kg cm2 for 10 hr at room temperature. Standard work-up yielded VII, which crystallized from Et.O-heximc, in a yield of 98.5 mg, as small needles: mp 182.5-184°c;" "1 ]740, 1720, 1710 (shi 1.
Durch aufeinanderfolgende Kondensationen von (I) mit (II) und (III) in Gegenwart von Natriumhydrid wurde der Ketoester (IV) erhalten und in Ameisensäure/Essigsäure in Gegenwart katalytischer Mengen Quecksilber(II)‐ Ionen mit Wasser zu (V) hydratisiert.
In' nuTvstallizaiimi from the same solvent systems liad rnp 130 132°: V™' 3263 (NR), 1690 (amide I), 1663 (0=0), 1613 and 1391) (0=0, and 1330 cm"1 (amide II); xRfJH 239 mg (e X I O'"3 = 17.8), 278 (18.6), and 433 (3.7).The 4-(3-.Y,.Y-diethylaniiiiop copy lamino )-3-acylamino-l .2naphthoqninones listed in Table I were synthesized by an analogous procedure.1 -(3'--Y,.V-Diethylaminopropyl )-2-pentylnaphth [ 1,2-t/J imidazole-4,5-dione (IVb).-A solution of 2.31 g, 6.1 mmol, of Illb in 200 ml of AcOH was refluxed for 0.3 hr. It was concentrated by freeze-dryiug and the remaining residue was chromatographed on 400 g of AbO,? using CHCfi as (he eluent. A red band was collected. Removal of the CHC1;1 on a rotary evaporator followed by recrystallization of the remaining red crystals from EtOAc gave 1.69 g (72r, ) of IYb, mp 138-141°. The analytical sample prepared bv recrystallization from EtOAc had mp 140-142°. rv") 1670 cnr1 (('=<)):
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.