Androsterone, structure

However, it should be noted that especially in the area of binding assays using labeled molecules, MIP-based assays already perform with similar efficiency as conventional immunoassays. A very recent application of MIP is their use to screen combinatorial libraries, e.g., for interactive molecules. Ramstrom et al used MIP imprinted with androsterone structures for selecting related compounds from a combinatorial steroid library. The molecules used as... 

Most steroids have an oxygen functional group (=0 or —OH) at C3 and some kind of side chain or other functional group at Cl7. Many also have a double bond from C5 to either C4 or C6. The structures of androsterone and cholesterol serve as examples. Androsterone, a male sex hormone, is based on the simple androstane ring system. Cholesterol is a common biological intermediate and is believed to be the biosynthetic precursor to other steroids. It has a side chain at C17 and a double bond between C5 and C6. 

Collection of the GC effluent and subsequent MS analysis allowed assignment of a possible molecular formula as Ci9H280. Since boar taint can be eliminated by castration of male pigs, attention was focused on the testosterone and androsterone family of compounds as possible candidates. When the crude volatiles were treated with 2,4-dinitrophenylhydrazine, the boar taint odor was completely removed, implicating a ketone functionality for the lone oxygen atom. Anecdotal information implicated several androstene derivatives, including 47, which was described as having an intense, urine-like odor. 143 An authentic sample of 47 was prepared, and comparison of the GC and MS properties allowed the definitive structural identification of the boar taint compound. 

Wieland, H., and Dane, E. Untersuchungen liber die Konstitution der Gal-lensauren. Uber den Aufbau des Gesamtgeriistes und liber die Natur von Ring D. [The constitution of bile acids. I. The structure of the entire framework and the nature of ring D.j Hoppe-Seylers Z. Physiol. Chem. 216, 91-104 (1933), Bernal, J. D., and Crowfoot, D. X-ray crystallographic data on the sex hormones, cestrone, androsterone, testosterone and progesterone and related substances. Z. Krist. A93, 464-480 (1936). 

Like the double bond, the carbon-carbon triple bond is susceptible to many of the common addition reactions. In some cases, such as reduction, hydroboration and acid-catalyzed hydration, it is even more reactive. A very efficient method for the protection of the triple bond is found in the alkynedicobalt hexacarbonyl complexes (.e.g. 117 and 118), readily formed by the reaction of the respective alkyne with dicobalt octacarbonyl. In eneynes this complexation is specific for the triple bond. The remaining alkenes can be reduced with diimide or borane as is illustrated for the ethynylation product (116) of 5-dehydro androsterone in Scheme 107. Alkynic alkenes and alcohols complexed in this way show an increased structural stability. This has been used for the construction of a variety of substituted alkynic compounds uncontaminated by allenic isomers (Scheme 107) and in syntheses of insect pheromones. From the protecting cobalt clusters, the parent alkynes can easily be regenerated by treatment with iron(III) nitrate, ammonium cerium nitrate or trimethylamine A -oxide. ° ... 

On the other hand, the quantitative prediction of competitive isotherm behavior for the components of binary mixtmes is not possible using the competitive Langmuir isotherm model when the difference between the column satmation capacities for the two components exceeds 5 to 10%. For example, the adsorption isotherms of pure cis- and trans-androsterone on sihca are well accoimted for by the Langmuir model [9]. However, the two column saturation capacities differ by 30%, due to the nearly flat structure of the trans isomer compared to the folded structure of the cis isomer. As a consequence, the competitive Langmuir model accounts poorly for the competitive adsorption data [9,10]. Much improved results are obtained with the more complex LeVan-Vermeulen isotherm (Section 4.1.5). Another approach could use the random adsorption site model, with different exclusion siuface areas for the competing molecules [12],... 

Androgens, the male sex hormones, proved far more elusive that either the estrogens and progestins since they occur at much lower concentrations in biological fluids. The bioassay used to track the isolation in this case comprised the capon unit . This was the amount of extract that produced a 20% increase in the surface of a rooster s comb. The 15 mg of pure crystalline testosterone isolated in 1931 came from about 15 0001 of urine. The structural investigations of this series relied on the then newly discovered side chain oxidations of cholestanol (13-1) (Scheme 1.13). This method in essence comprised fairly drastic oxidation of reduced cholesterols of known stereochemistry at the A-B junction to afford in fairly low yield products in which the side chain at Cn had been consumed to leave behind a carbonyl group. One of these products proved to be identical with androsterone (13-2). That compound had in turn been obtained from a sequence of reactions starting from dehydroepiandrosterone (13-3) that had been isolated from male urine. 

Adolf Friedrich Johann Butenandt (1903-1995) was born in Germany. He shared the 1939 Nobel Prize in chemistry (withRuzicka seep. 14 for isolating and determining me structures of estrone, androsterone, and progesterone. Forced by the Nazi government to refuse the prize, he accepted it after World War II. He was the director of the Kaiser Wilhelm Institute in Berlin and later was a professor at the Universities of Tubingen and Munich. 

A number of studies have been carried out on large molecules, particularly in the steroid area. Accurate structures for a number of steroids are now becoming available through x-ray studies. We might consider the structure of androsterone [4] as an example of such an... 

FIGURE 3.4 Structures of endogenous compounds involved in glucuronidation bile adds, lithocholic add (LA) and hyodeoxycholic acid (HDCA) short chain bile acids, etianic add and isoetianic add, steroid hormones, androsterone, testosterone, estrone, estradiol, estriol. 

Androgens a group of male gonadal hormones, including testosterone, androsterone and androsteno-lone, which are formed in the intermediary cells of the testes tissue, and a number of less active A. produced in the adrenal cortex, e.g. androstenedione and adrenosterone (Fig.). Since A. are precursors of Estrogens (see), they are also synthesized in the ovaries and fetoplacental unit. At present more than 30 naturally occurring A. are known, all structurally related to the parent hydrocarbon, androstane (see Steroids). 

Several structures of two steroids, androsterone and beclomethasone dipropionate, have been characterised by sohd-state NMR and powder XRD methods, and the chemical shifts between the different forms compared. ... 

The same fused, four-ring core structure is present in the steroids, which have different biological roles as hormones and signaling molecules. The C18 steroids include the estrogen family, whereas the C19 steroids constitute the androgens, such as testosterone and androsterone. The C21 subclass includes the progestogens, the glucocorticoids, and mineralocorticoids. 

Figure 3.6 Structures of selected steroidal compounds testosterone (1), 5a-dihydrotestosterone (2), androsterone (3),etiocholanolone (4), 1-dehydrotestosterone (5), androsta, 6-dien-17p-ol-3-one (6), and 17a-methylandrosta-4,9(ll)-dien-17P-ol-3-one (7).

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