合成路线:The title compound was prepared by dehydration of 11-hydroxyl group of hydrocortisone acetate (I) by means of methanesulfonyl chloride and pyridine in hot DMF.Dehydration of (I) has also been reported by treatment with N,N'-sulfinyldiimidazole,prepared from imidazole and thionyl chloride.
参考文献标题:Process for preparing useful 17alpha-hydroxy-20-keto-21-acyloxy pregnanes
文献作者:Crabbe,P.; Biollaz,M.S.(Syntex (USA) LLC)
参考来源:US 3658856
合成路线:The title compound was prepared by dehydration of 11-hydroxyl group of hydrocortisone acetate (I) by means of methanesulfonyl chloride and pyridine in hot DMF.Dehydration of (I) has also been reported by treatment with N,N'-sulfinyldiimidazole,prepared from imidazole and thionyl chloride.
参考文献标题:Process for preparing 17alpha-hydroxy-20-keto and 17alpha,21-dihydroxy-20-keto pregnanes and derivs.and intermediates thereof
文献作者:Crabbe,P.; Velarde,E.(Syntex (USA) LLC)
参考来源:US 3681410
合成路线:Reaction of 9a-hydroxyandrost-4-ene-3,17-dione (I) with benzenesulfinyl chloride and pyridine gives the corresponding sulfinate (II),which by treatment with TsOH in refluxing chloroform yields androsta-4,9(11)-diene-3,17-dione (III).Reaction of the androstadienedione (III) with acetylene by means of potassium tert-butoxide in THF affords the 17a-ethynyl derivative (IV),which is treated with phenylsulfenyl chloride and TEA at ?0 C to provide the sulfenate ester (V).Rearrange-ment of sulfenate (V) by warming at ?0 C gives the allene sulfoxide (VI),which is treated with sodium methoxide in methanol at 25 C to yield the enol ether sulfoxide (VII).Then,by refluxing in methanol,an equilibrium between sulfoxide (VII) and sulfenate (VIII) occurs.Reaction of the non-isolated sulfenate (VIII) with the thiophile trimethyl phosphite affords the 17a-hydroxy enol ether (IX),which is finally converted to anecortave acetate by either treatment with peracetic acid and NaHCO3 in dichloromethane or bromination with Br2 and pyridine in dichloromethane to give compound (X) followed by treatment with KOAc,KI and AcOH in refluxing acetone.
参考文献标题:Process for the preparation of 17alpha-hydroxyprogesterones and corticoids from androstenes
文献作者:Shephard,K.P.; Van Rheenen,V.H.(Pharmacia Corp.)
参考来源:US 4041055
合成路线:Condensation of 3-methoxyandrosta-3,5,9(11)-trien-17-one (XI) with (E)-1,2-dichloroethylene (XII) by means of BuLi in toluene gives 17a-[(E)-1,2-dichloro-vinyl]-17b-hydroxyandrosta-4,9(11)-dien-3-one (XXX),which is treated with phenylsulfenyl chloride and TEA in dichloromethane to yield 20,21-dichloro-21-(phenylsulfinyl)pregna-4,9(11),17(20)-trien-3-one (XXXI).Reac-tion of compound (XXXI) with MeONa in acetone/MeOH at 0 C affords 21-chloro-20-methoxy-21-(phenylsulfinyl)-pregna-4,9(11),17(20)-trien-3-one (XXXII),which by treatment with more MeONa at 35 C provides 21-chloro-17a-hydroxy-20-methoxypregna-4,9(11),20-trien-3-one (XXXIII).Hydrolysis of the enol ether of (XXXIII) with HCl in THF/acetone/MeOH gives the 3,20-dione derivative (XVI),which is finally treated with AcOK and KI in hot acetone/dichloromethane.
参考文献标题:Preparation of corticoids from 17-keto steroids
文献作者:Walker,J.A.; Hessler,E.J.(Pharmacia Corp.)
参考来源:US 4357279
合成路线:Condensation of 3-methoxyandrosta-3,5,9(11)-trien-17-one (XI) with 3-hydroxypropionitrile (XXV) by means of LDA in THF provides 17a-(1-cyano-2- hydroxyethyl)-17b-hydroxyandrosta-4,9(11)-dien-3-one (XXVI),which is selectively monoacetylated by means of Ac2O in pyridine to yield monoacetate (XXVII).Dehydration of (XXVII) by means of SOCl2 in pyridine gives 20-cyano-21-acetoxypregna-4,9(11),17(20)-trien-3-one (XXVIII),which is treated with ethylene glycol,trimethyl orthoformate and TsOH in dichloromethane to afford the ethylene ketal (XXIX).Finally,compound (XXIX) is oxidized with KMnO4 in acetone/ethylene glycol and treated with NaHSO3 and HCOOH.
参考文献标题:Corticosteroids from 17-keto steroids via 20-cyano-DELTA17(20)-pregnanes
文献作者:Walker,J.A.(Pharmacia Corp.)
参考来源:US 4600538
合成路线:In a different approach,irradiation of (IX) in the presence of phenyliodine dichloride produced selectively the 9-chloro derivative (X).This was dechlorinated to the 9(11) olefin (XI) with AgBF4 in acetone.Hydrolysis of the ester groups of (XI) by K2CO3 in MeOH afforded diol (XII),which was finally converted to the title compound by selective reacetylation of the C-21 hydroxyl group.
参考文献标题:Selective chlorination of steroids and other substrates directed by covalently linked agents comprising a nitrogen-containing ring acting as templates
文献作者:Breslow,R.; Brandl,M.; Adam,A.D.; Hunger,J.(Columbia University)
参考来源:WO 8809337
产品链接: CAS No. 7753-60-8››