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Mass spectra and fragmentation patterns of the epimeric 17-, 16-, 15- and 14-hydroxy derivatives of 3-methoxy-1,3,5(10)-estratriene are compared. The main fragmentation pathways are differently influenced, depending on the position of the hydroxy group. The different configuration of the hydroxy groups is reflected only in the spectra of the epimeric 15- and 14-hydroxy compounds. Possibilities of mass spectrometric differentiation between the hydroxyestratrienes are discussed. 相似文献
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The conjugate hydrocyanation of 17-acetylgona-11-carbomethoxy-1,3,5(10),13(17)-tetraenes using diethylaluminum cyanide (Nagata reaction) is reported. This methodology has allowed the introduction of an angular cyano group at the C-13 position of the steroid skeleton. Subsequent reduction of the nitrile group yielded various functionalized steroids. One of them, 22 bears the natural trans/anti/trans stereochemistry and possesses an hydroxyl and aminomethyl functionalities in the positions 11beta and 13beta, respectively. The characteristic (1)H and (13)C NMR spectroscopic features of the synthesized steroids are reported. 相似文献
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Golubovskaia LE Smirnova ZS Tolkachev VN Rzheznikov VM 《Bioorganicheskaia khimiia》2006,32(2):221-223
Esterification of 3-hydroxyl group in 11-acyloxyestra-1,3,5(10)-trienes with p-[bis(2-chloroethyl)amino]phenylacetic acid led to antitumor steroids displaying antiestrogenic and cytotoxic activities. Our substances exhibit their activities on the model of murine mammary adenocarcinoma Ca-755, with inhibition of the tumor growth being 94-99%. A new approach was used for the 11alpha-hydroxylation of estra-1,3,5(10)-trienes. 相似文献
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Parameters for microbial transformation of 13-ethyl-3-methoxy-8, 14-seco-gona-1,3,5 (10), 9(11)-tetraene-14,17-dione to its 17 beta-hydroxy derivative by P. farinosa have been standardised in pilot plant fermentors. The yield of the pure crystalline compound was 80%. 相似文献
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S Schwarz M Schumacher S Ring A Nanninga G Weber I Thieme B Undeutsch W Elger 《Steroids》1999,64(7):460-471
The title compound 17 has been synthesized for the use as hapten in the development of a competitive enzyme immunoassay for estrogen sulfamates. The synthesis started from estradiol diacetate 2. Oxyfunctionalization at C-11 to give 11alpha-hydroxy steroid 8 was accomplished by hydroboration/alkaline hydrogen peroxide oxidation of the 9(11)-dehydro derivative 7, which was obtained from compound 2 via 9-hydroxylation with dimethyldioxirane. After transformation of compound 8 into the allyl ether 9, the side chain was thio-functionalized at the omega-position affording the thioate 11 in two steps. Selective silylether deprotection at position 3 followed by sulfamoylation gave the sulfamate 19, which in turn was demasked at position 17 and treated with sodium borohydride/aluminum chloride to liberate the side chain thiol. Alternatively, title compound 17 was synthesized via the disulfides 13-16. For the preparation of the immunogen the title compound 17 was coupled to bovine gamma globulin in a two-step procedure using an amine and thiol specific bifunctional crosslinker. The immunization of rabbits resulted in the formation of antibodies which clearly discriminated the sulfamoylated estrogens from the non-esterified estrogens. The use of a biotinylated hapten derivative as a tracer in combination with a streptavidin-peroxidase-tetramethylbenzidine based detection system allowed the measurement of estradiol 3-sulfamate (1) in the range of about 1 to 1000 pg/well. 相似文献
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We set out to describe a new and versatile method for preparing 3-aza-11-oxa-1,3,5(10)-trieno steroids via an intramolecular Diels-Alder cycloaddition of o-quinodimethanes as the key step. The characteristic 1H and 13C NMR spectroscopic features of the synthesized compounds are reported. 相似文献
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The conversion of estrone to 14,15-secoestratrien-15-ynes, inactivators of estradiol dehydrogenase from human term placenta, is described. The optically pure precursor 7-acetoxy-octahydro-2-phenanthrenecarboxylic acid methyl ester is prepared from estrone in five steps and 40% yield. The unsubstituted propargylic secoestratriene diol, a mechanism-based inactivator of estradiol dehydrogenase, and the corresponding acetylenic ketone, an affinity label inactivator of the same enzyme, arise from the phenanthrene ester in three and four steps. The propargylic secoestratriene diol also competes with [3H]estradiol for binding to calf uterus estrogen receptor and possesses weak uterotrophic activity. 相似文献
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We described an efficient synthesis of (8β,9β,14β)-17β-acetyl-13β-p-bromophenyl-11,11-di(methoxycarbonyl)-3-methoxygona-1,3,5(10)-triene, (8β,9α,14β)-17β-acetyl-13β-p-bromophenyl-11,11-di(methoxycarbonyl)-3-methoxygona-1,3,5(10)-triene, (8β,9β,14β)-13 β-p-bromophenyl-11,11-di(methoxycarbonyl)-17β-(2-hydroxyethyl)-3-methoxygona-1,3,5(10)-triene, and (8β,9β,14β)-13β-p-bromophenyl-11,11-di(methoxycarbonyl)-17β-(2-oxoxyethyl)-3-methoxygona-1,3,5(10)-triene in five or six steps from 1-iodo-4-methoxybenzocyclobutene and readily available materials. 相似文献