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1.
A large number of esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) and levonorgestrel (D-(-)-13β-ethyl-17α-ethynyl-17β-hydroxygon-4-en-3-one) were synthesized and tested for biological activity. The test employed in these studies was the duration of estrus suppression in cycling mature rats. In the norethisterone series several esters exhibited duration of activity comparable to that of norethisterone enarthate. In the levonorgestrel series the butanoic, cyclobutylcarboxylic and cyclopropylcarboxylic esters were longer acting than medroxyprogesterone acetate (17α-acetoxy-6α-methylpregn-4-ene-3, 20-dione) when prepared as aqueous microcrystalline suspensions. 相似文献
2.
A. Shafiee M. Vossoghi F. Savabi T.G. Watson K. Schubert K. Ponsold W. Werner H. Wagner R. Vlahov V. Tarpanov M. Boshkova-Ljapova B. Milenkov V. Stoilova J. Vlahov G. Snatzke H. Duddeck 《Steroids》1983,41(3):349-359
Esters of levonorgestrel (13β-ethyl-17α-ethynyl-17β-hydroxygon-4-en -3-one) with a variety of aliphatic and alicyclic carboxylic acids have been prepared and characterised. In tests for the suppression of estrus in rats, esters with short-chain aliphatic acids and with cyclobutane-carboxylic acid were considerably more active than the standard, norethisterone enanthate (17α-ethynyl-17β-hydroxyestr-4-en-3-one). Such esters show great promise for development as long-acting progestogens. 相似文献
3.
A. Shafiee M. Vossoghi F. Savabi R. Vlahov V. Tarpanov M. Boshkova-Ljapova B. Milenkov V. Stoilova J. Vlahov G. Snatzke 《Steroids》1983,41(3):291-307
Several esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) with carboxylic acids containing a cyclopropyl or cyclobutyl ring have been synthesized and the stereochemistries of the side-chains determined. 相似文献
4.
A. Shafiee M. Vossoghi C.G. Francisco R. Freire R. Hernandez J.A. Salazar E. Suarez S. Sotheeswaran 《Steroids》1983,41(3):285-290
The chemical synthesis and physical data of several new esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) are reported, which contain either a chloro- or an alkoxy-group as a substituent in the acid side-chain. 相似文献
5.
A.S.C. Wan T.L. Ngiam S.L. Leung M.L. Go P.W.S. Heng P.N. Natarajan A. Shafiee M. Vossoghi F. Savabi C.G. Francisco R. Freire R. Hernandez J.A. Salazar E. Suarez G.A.Garcia De La Mora Y.Grillasca R. O. Jimeno 《Steroids》1983,41(3):309-320
The synthesis of esters of norethisterone (17α-ethynyl-17β-hydroxy-estr-4-en-3-one) with acids containing a benzene ring is described, two methods of esterification being compared in terms of yield and convenience. The activities of these esters as long-acting contraceptive agents have been evaluated. 相似文献
6.
A.S.C. Wan T.L. Ngiam S.L. Leung M.L. Go C.G. Francisco R. Freire R. Hernandez J.A. Salazar E. Suarez G.A. Garcia O. Jimeno J.A.Noguez A. A.Acosta H. R. Vlahov V. Tarpanov M. Boshkova-Ljapova B. Milenkov V. Stoilova G. Snatzke 《Steroids》1983,41(3):339-348
Esters of levonorgestrel (13β-ethyl-17β-ethynyl-17β-hydroxygon-4-en-3-one) with a variety of unsaturated carboxylic acids have been synthesized for evaluation as potential long-acting, injectable contraceptive agents. 相似文献
7.
The potential for biotransformation of the substrate 17β-hydroxyandrost-4-en-3-one (testosterone) by six filamentous fungi, namely, Rhizopus oryzae ATCC 11145, Mucor plumbeus ATCC 4740, Cunninghamella echinulata var. elegans ATCC 8688a, Aspergillus niger ATCC 9142, Phanerochaete chrysosporium ATCC 24725 and Whetzelinia sclerotiorum ATCC 18687, was investigated. In this study both free cells and macerated mycelia immobilised in calcium alginate were utilised and the results (products, % yields, % transformation) were compared. In general the encapsulated cells of the microorganisms effectively generated products similar to those found using free cells. However, with immobilised macerated mycelia, isolation of the transformation products was expedited by the simple work up procedure, and their purification was facilitated by the absence of fungal secondary metabolites. Twenty seven analogues of testosterone were generated, wherein the androstane skeleton was functionalised at C-1β, -2β, -6β, -7α, -11α, -14, -15α, -15β and -16β by the moulds. Redox chemistry was also observed. Seven of the analogues, 6β,11α,17β-trihydroxyandrost-4-en-3-one, 6β,14α,17β-trihydroxyandrost-4-en-3-one, 2,6β-dihydroxyandrosta-1,4-diene-3,17-dione, 2β,16β-dihydroxyandrost-4-ene-3,17-dione, 2β,6β-dihydroxyandrost-4-ene-3,17-dione, 2β,15β,17β-trihydroxyandrost-4-en-3-one and 2β,3α,17β-trihydroxyandrost-4-ene, were novel compounds. Five others, namely, 7α,17β-dihydroxyandrost-4-en-3-one, 6β,14α-dihydroxyandrost-4-ene-3,17-dione, 15α,17β-dihydroxyandrost-4-en-3-one, 16β,17α-dihydroxyandrost-4-en-3-one and 2β,16β,17β-trihydroxyandrost-4-en-3-one, were fully characterised for the first time. 相似文献
8.
Sobolevsky T Rodchenkov G 《The Journal of steroid biochemistry and molecular biology》2012,128(3-5):121-127
The biotransformation of dehydrochloromethyltestosterone (DHCMT, 4-chloro-17β-hydroxy,17α-methylandrosta-1,4-dien-3-one) in man was studied with the aim to discover long-term metabolites valuable for the antidoping analysis. Having applied a high performance liquid chromatography for the fractionation of urinary extract obtained from the pool of several DHCMT positive urines, about 50 metabolites were found. Most of these metabolites were included in the GC-MS/MS screening method, which was subsequently applied to analyze the post-administration and routine doping control samples. As a result of this study, 6 new long-term metabolites were identified tentatively characterized using GC-MS and GC-MS/MS as 4-chloro-17α-methyl-5β-androstan-3α,16,17β-triol (M1), 4-chloro-18-nor-17β-hydroxymethyl,17α-methyl-5β-androsta-1,13-dien-3α-ol (M2), 4-chloro-18-nor-17β-hydroxymethyl,17α-methyl-5β-androst-13-en-3α-ol (M3), its epimer 4-chloro-18-nor-17α-hydroxymethyl,17β-methyl-5β-androst-13-en-3α-ol, 4-chloro-18-nor-17β-hydroxymethyl,17α-methylandrosta-4,13-dien-3α-ol (M4) and its epimer 4-chloro-18-nor-17α-hydroxymethyl,17β-methylandrosta-4,13-dien-3α-ol. The most long-term metabolite M3 was shown to be superior in the majority of cases to the other known DHCMT metabolites, such as 4-chloro-18-nor-17β-hydroxymethyl,17α-methylandrosta-1,4,13-trien-3-one and 4-chloro-3α,6β,17β-trihydroxy-17α-methyl-5β-androst-1-en-16-one. 相似文献
9.
A series of 7α- and 7β- alkyl derivatives of steroidal 4-en- and 5-en-3-ones were prepared by 1,6-conjugate addition of organocopper reagents to various steroidal 4,6-dien-3-ones of the androstane, estrane and gonane series. Biological study of these and related compounds revealed that 17β-hydroxy-7α-methyl-5-androsten-3-one (2), 17β-hydroxy-7α-methyl-5-estren-3-one acetate and 17β-hydroxy-7α-methyl-4-estren-3-one acetate had significant anti-implantational and antidecidual activities. The contragestative effects were associated with the latter antihormonal properties, and not with the androgenicity of these compounds. 相似文献
10.
17β-esters of norethisterone (17α-ethynyl-17β-hydroxyestr-4-en-3-one) have been formulated as aqueous microcrystalline suspensions and oily solutionsfor administration to rats to assess the length of progestogenic activity. Results show that, for some of the esters, the rate-controlling step in prolonging activity is the rate of drug release from the injected formulation. For these esters, when formulated as suspensions, it is proposed that crystal size and form will have a critical effect upon duration of estrus suppression. The influence of crystal form has been demonstrated with the 4-(butoxy)phenylacetate ester for which two different crystal forms have been identified. The lower melting point, more soluble crystal form shows marked prolongation of action, whereas the other form is ineffective. 相似文献
11.
- 1.1. The major aglycones produced by acid hydrolysis of the saponins from the starfish Astropecten aurantiacus are identified as 3β,6α-dihydroxy-5α-pregn-9(11)-en-20-one (1), (17 E)- and (17 Z)-3β,6α-dihydroxy-5α-cholesta-9(11),17(20)-dien-23-one (9 and 10), (17 E)- and (17 Z)-3β,6α-dihydroxy-5α-cholesta-9(11), 17(20),24-trien-23-one (11 and 12), (20 E)-3β,6α-dihydroxy-5α-cholesta-9(11),20(22)-dien-23-one (4), and 17β-methyl-3β,6α-dihydroxy-18-nor-5α-cholesta-9(11),13-dien-23-one (13).
- 2.2. A re-examination of the sapogenins from the starfish Marthasterias galcialis, in addition to the previously isolated 1, 3β,6α-dihydroxy-5α-cholesta-9(11)-en-23-one (2, dihydromarthasterone), 3β,6αdihydroxy-5α-cholesta-9(11),24-dien-23-one (3, marthasterone) and 3β,6α-dihydroxy-5α-chol-9(11)-en-23-one (14), has shown the presence of minor amounts of 9, 10, 4 and 13.
- 3.3. A [13C]NMR study of the major sapogenins, 9 and 10, from A. aurantiacus, and 1, 2 and 14 from M. glacialis is also reported.
12.
R. P. Litvinovskaya A. V. Baranovsky M. A. Averkova V. A. Khripach 《Russian Journal of Bioorganic Chemistry》2007,33(3):320-325
Androstane and Δ15-androstane analogues of brassinosteroids were synthesized from dehydroepiandrosterone. The key stage, hydroxylation of 17β-acetoxyandrost-2-en-6-one double bond with OsO4, yielded the corresponding 2α,3α-and 2β,3β-diols. The target 2α,3α-isopropylidenedioxy-6,6-ethylenedioxy-5α-androst-15-en-17-one and its 2β,3β-isomer were obtained by dehydrosilylation of the corresponding silylenol ethers with palladium acetate. 相似文献
13.
Claude-Yves Cuilleron Elisabeth Mappus Maguelone G. Forest Jean Bertrand 《Steroids》1981,38(6):607-632
The reduction of 3-ethylenedioxy-7-oximino-5-androsten-17β-yl acetate and of its 17β-tetrahydropyranyl ether analog with sodium in ethanol, followed by thin-layer chromatography, allowed the isolation of the corresponding 17β-hydroxy- and 17β-tetrahydropyranyioxy-5-en-7β- and 7α-amines which were also characte-rized as 7-acetamides. The acylation of the two epimeric 17β-hydroxy-5-en-7-amines with succinic anhydride followed by selective saponification of the 17β-hemisuccinate group and diazomethane esterification, gave the corresponding 17β-hydroxy-5-en-7β- and 7α-hemisuccinamido methyl esters characterized also as 17β-acetates. On the other hand, the acylation of the two 17β-tetrahydropyranyl-oxy-5-en-7-amines with the acid chloride of terephthalic acid monomethyi ester led to the more rigid 7β- and 7α-terephthalamido methyl ester side-chains. The acidolysis of the 3-ethyleneketal protecting group of the preceding 5-en-7-N-acyl derivatives regenerated the 4-en-3-oxo function while the 17β-tetrahydropyranyl ether group was cleaved simultaneously into the 17β-alcohol. The four desired 7β- and 7α-hemisuccinamido- and terephthalamido carboxylic side-chain derivatives of 17β-hydroxy-4-androsten-3-one (testosterone) were finally obtained by saponification of the corresponding methyl esters. 相似文献
14.
The photosensitized oxidation of cholest-4-en-3β-ol in which singlet molecular oxygen is implicated yielded cholest-4-en-3-one and the isomeric epoxides 4α,5-epoxy-5α-cholestan-3-one and 4β,5-epoxy-5β-cholestan-3-one, the epoxides being formed in the ratio 3 : 1. Oxidation of cholest-4-en-3-one by alkaline hydrogen peroxide likewise yielded the isomeric 4,5-epoxides but in the ratio 1 : 7.4. Attempted use of cholest-4-en-3β-ol to intercept singlet molecular oxygen putatively generated in the disproportionation of hydrogen peroxide gave a very complex product mixture of over 50 components from which only cholest-4-en-3-one could be identified. However, neither isomeric 4,5-epoxycholestan-3-one was detected among the products. These data establish that it is unwarranted to infer the action of single molecular oxygen in systems containing cholest-4-en-3β-ol merely by product analysis where the product 4α,5-epoxy-5α-cholestan-3-one is formed. 相似文献
15.
From the extract of the fruits of Solanum xanthocarpum (Solanaceae), five new steroidal compounds were isolated and characterized: 4α-methyl-24ξ-ethyl-5α-cholest-7-en-3β,22ξ-diol (1), 3β,22ξ-dihydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (2), 3β-benzoxy-14β,22ξ-dihydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (3), 3β-benzoxy-14α,22ξ-dihydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (4) and 3β-(p-hydroxy)-benzoxy-22ξ-hydroxy-4α-methyl-24ξ-ethyl-5α-cholest-7-en-6-one (5). 相似文献
16.
Parr MK Opfermann G Geyer H Westphal F Sönnichsen FD Zapp J Kwiatkowska D Schänzer W 《Steroids》2011,76(6):540-547
New analogues of androgens that had never been available as approved drugs are marketed as “dietary supplement” recently. They are mainly advertised to promote muscle mass and are considered by the governmental authorities in various countries, as well as by the World Anti-doping Agency for sport, as being pharmacologically and/or chemically related to anabolic steroids.In the present study, we report the detection of a steroid in a product seized by the State Bureau of Criminal Investigation Schleswig-Holstein, Germany. The product “1-Androsterone” of the brand name “Advanced Muscle Science” was labeled to contain 100 mg of “1-Androstene-3b-ol,17-one” per capsule. The product was analyzed underivatized and as bis-TMS derivative by GC-MS. The steroid was identified by comparison with chemically synthesized 3β-hydroxy-5α-androst-1-en-17-one, prepared by reduction of 5α-androst-1-ene-3,17-dione with LS-Selectride (Lithium tris-isoamylborohydride), and by nuclear magnetic resonance. Semi-quantitation revealed an amount of 3β-hydroxy-5α-androst-1-en-17-one in the capsules as labeled.Following oral administration to a male volunteer, the main urinary metabolites were monitored. 1-Testosterone (17β-hydroxy-5α-androst-1-en-3-one), 1-androstenedione (5α-androst-1-ene-3,17-dione), 3α-hydroxy-5α-androst-1-en-17-one, 5α-androst-1-ene-3α,17β-diol, and 5α-androst-1-ene-3β,17β-diol were detected besides the parent compound and two more metabolites (up to now not finally identified but most likely C-18 and C-19 hydroxylated 5α-androst-1-ene-3,17-diones). Additionally, common steroids of the urinary steroid profile were altered after the administration of “1-Androsterone”. Especially the ratios of androsterone/etiocholanolone and 5α-/5β-androstane-3α,17β-diol and the concentration of 5α-dihydrotestosterone were influenced. 3α-Hydroxy-5α-androst-1-en-17-one appears to be suitable for the long-term detection of the steroid (ab-)use, as this characteristic metabolite was detectable in screening up to nine days after a single administration of one capsule. 相似文献
17.
Progesterone-4-14C was extensively metabolized during incubation with dispersed trophoblast prepared from chorionic membranes of the 21-day sheep conceptus. Of the metabolites formed, 17,20α-dihydroxypregn-4-en-3-one, 20α-hydroxypregn-4-en-3-one, 20(β-hydroxypregn-4-en-3-one, 5α-pregnane-3α,17,20α-triol, 5β-pregnane-3ga, 17,20α-triol, 5β-pregnane-3g,20α-diol, 3β-hydroxy-5α-pregnan-20-one, 3α-hydroxy-5β-pregnan-20-one, 20β-hydroxy-5β-pregnan-3-one, 5α-pregnane-3,20-dione and 5β-pregnane-3,20-dione were identified. These findings indicate that the sheep conceptus acquires extensive steroid metabolizing capability very early in pregnancy. 相似文献
18.
The synthesis of 3β-hydroxy-androsta-5,7-dien-17-one from 3β-hydroxy-androst-5-en-17-one (dehydroepiandrosterone, DHEA) via microbial 7α-hydroxylation has been accomplished. At the first stage, 3β,7α-dihydroxy-androst-5-en-17-one was obtained in high yield (71.2%) using a strain of Gibberella zeae VKM F-2600, which was first applied for DHEA conversion. The further route included the substitution of 7α-hydroxyl group with chlorine followed by a dehydrochlorination stage, and required minimal purifications of the intermediate products. The steroids obtained at every step were characterized by TLC,1H NMR, MS, UV- and IR-spectrometry.The combination of microbial and chemical steps ensured 54.6% yield of the target 3β-hydroxy-androsta-5,7-dien-17-one from DHEA and can be applied for obtaining novel vitamin D derivatives. 相似文献
19.
《Fungal biology》2022,126(1):91-100
Fungal strain Drechslera sp. Ph F-34 was shown to modify 3-oxo- and 3-hydroxy steroids of androstane series to form the corresponding allylic 7-alcohols and 17β-reduced derivatives thus evidencing the presence of 7α-, 7β-hydroxylase and 17β-hydroxysteroid dehydrogenase (17β-HSD) activities. The growing mycelium predominantly hydroxylated androsta-1,4-diene-3,17-dione (ADD) at the 7β-position, while much lower 7α-hydroxylation was observed. Along with 7β-hydroxy-ADD and its corresponding 7α-isomer, their respective 17β-alcohols were produced.In this study, transformation of ADD, androst-4-en-17β-ol-3-one (testosterone, TS) and 3β-hydroxyandrost-5-en-17-one (dehydroepiandrosterone, DHEA) by resting mycelium of Drechslera sp. have been estimated in different conditions with regard to the inducibility and functionality of the 17β-HSD and 7-hydroxylase enzyme systems. Steroids of androstane, pregnane and cholane series were evaluated as inducers. The inhibitory analysis was provided using cycloheximide (CHX). Steroids were assayed using TLC and HPLC methods, and the structures were confirmed by mass-spectrometry, 1H and 13C NMR spectroscopy data.17β-HSD of the mycelium constitutively reduced 17-carbonyl group of ADD and DHEA to form the corresponding 17β-alcohols, namely, androsta-1,4-diene-17β-ol-3-one (1-dehydro-TS), and androst-5-ene-3β,17β-diol. Production of the 7α- and 7β-hydroxylated derivatives depended on the induction conditions. The inducer effect relied on the steroid structure and decreased in the order: DHEA > pregnenolone > lithocholic acid. β-Sitosterol did not induce hydroxylase activity in Drechslera sp. CHX fully inhibited the synthesis of 7-hydroxylase in Drechslera mycelium thus providing selective 17-keto reduction.Results contribute to the diversity of steroid modifying enzymes in fungi and can be used at the development of novel biocatalysts for production of valuable steroid 7(α/β)- and 17β-alcohols. 相似文献
20.
Sertoli cells isolated from 17 day old rats were maintained in culture and incubated with [14C]-progesterone for 20 h. The cells and media were extracted with ether/chloroform and the extracts chromatographed two-dimensionally on TLC and the radioactive metabolites visualized by autoradiography. Nine of the metabolites (constituting about 88% of total metabolite radioactivity) were identified by relative mobilities of the compounds and their derivatives in TLC and GC systems and by recrystallizations with authentic steroids as the following: 20α-hydroxypregn-4-en-3-one, 3α-hydroxy-5α-pregnan-20-one, 5α-pregnane3α,20α-diol, 17β-hydroxy-5α-androstan-3-one, 5α-pregnane-3,20-dione, 17-hydroxypregn-4-ene-3,20-dione, testosterone, 5α-androstane-3α,17β-diol and androst-4-ene-3,17-dione. Over 71% of the metabolite radioactivity was due to 20α-hydroxypregn-4-en-3-one, the major metabolite. 5α-reduced pregnanes constituted about 12% and C19 steroids comprised about 2.9% of the radioactivity of the metabolites. Calculation of relative steroidogenic enzyme activities from initial reaction rates suggested the following activities in μunits/mg Sertoli cell protein: 20α-hydroxysteroid oxidoreductase (20α-HS0; 7.71), 5α-reductase (4.77), 3α-HS0 (3.57), 17α-hydroxylase (0.93), 17β-HS0 (0.34) and C17-C20 lyase (0.34). The relatively high rate of steroidogenic enzyme activities in the Sertoli cells of young rats may indicate that Sertoli cells are less dependent on Leydig cell steroidogenesis than has been assumed. Since nearly all the metabolites of progesterone and testosterone are now identified, it is possible to construct a picture of Sertoli cell steroidogenic activity. 相似文献