Mass Spectrometry in Structural and Stereochemical Problems. XIV.1 Steroids with One or Two Aromatic Rings2

Djerassi, Carl; Wilson, Jennifer M.; Budzikiewicz, H.; Chamberlin, James W.

doi:10.1021/ja00882a034

Cited by 76 publications

(28 citation statements)

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“…Other characteristic fragment ions, including those at m/z 211, 183, 147, and 122, which appear to arise from the EQ moiety, are relatively minor. The ions at m/z 211 and 183 have also been observed and discussed in previous studies of EI mass spectrum of EQ [38]. The fragment ions at m/z 147 and 122 are likely formed by cleavage of C and B rings, respectively, followed by hydrogen rearrangement.…”

Section: Lc-esi-ms/ms Of the Ps Derivatives Of E1 Ee2 Eq And Eqnsupporting

confidence: 56%

“…The ions at m/z 146, 172, 185 and 213 all appear to arise from E1, and all are also prominent in the EI spectrum of E1 [41]. Their formation has been discussed in detail in earlier reports [38][39][40][41]. The product ion spectrum of the PS derivative of EE2 shows a significant peak at m/z 374, assigned to [M+H−SO 2 ] + , while the radical EE2 cation at m/z 296 and the radical pyridinium ion at m/z 79 are of relatively low intensity (Fig.…”

Section: Lc-esi-ms/ms Of the Ps Derivatives Of E1 Ee2 Eq And Eqnmentioning

confidence: 78%

“…3) appear to represent cleavages of the steroid C and D rings. In analogy to the EI spectrum of E2, the formation of the ion at m/z 172 may be produced by the cleavage of the C and D rings with hydrogen migration, and the peak at m/z 146 may be produced by cleavage of the C ring, as has been proposed [38,39].…”

Section: Lc-es-ms 3 Of the Ps Derivative Of E2mentioning

confidence: 91%

“…4B). The base peak in the spectrum of the PS derivative of EE2 is at m/z 213, and is thought to arise from a D ring cleavage (Scheme 3) [38] as discussed above.…”

Section: Lc-esi-ms/ms Of the Ps Derivatives Of E1 Ee2 Eq And Eqnmentioning

confidence: 96%

“…Based on extensive studies of the EI mass spectra of underivzatized estrogens and estrogen analogs [38][39][40][41], several fragmentation pathways were proposed by these previous authors, leading to the structural assignments for prominent ions depicted in Scheme 3. The peak at m/ z 254, one that is prominent in the MS 3 spectrum of the PS derivative of E2 but is of very low intensity in the EI spectrum of E2, is most likely formed by the loss of H 2 O from the C-17 hydroxyl group, a process that may be more favorable in CID rather than in EI-induced fragmentation.…”

Section: Lc-es-ms 3 Of the Ps Derivative Of E2mentioning

confidence: 99%

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Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Spink

2008

Analytical Biochemistry

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Sulfonyl chlorides substituted with functional groups having high proton affinity can serve as derivatization reagents to enhance the sensitivity for steroidal estrogens in liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS). The most commonly used reagent for derivatization of estrogens for LC-ESI-MS/MS is dansyl chloride. In this study, we compared dansyl chloride, 1,2-dimethylimidazole-4-sulfonyl (DMIS) chloride, pyridine-3-sulfonyl (PS) chloride, and 4-(1H-pyrazol-1-yl)benzenesulfonyl (PBS) chloride for derivatization of 17β-estradiol (E2) prior to LC-ESI-MS/MS. The product ion spectra of the dansyl and DMIS derivatives were dominated by ions representing derivatization reagent moieties. In contrast, the product ion spectrum of the PS derivative of E2 and, to a lesser extent, the PBS derivative, showed analytespecific fragment ions. Derivatization with PS chloride was therefore chosen for further investigation. The product ion spectrum of the PS derivative of E2 showed intense ions at m/z 272, assigned to the radical E2 cation, and at m/z 350, attributed to the loss of SO 2 from the [M+H] + ion. Third-stage mass spectrometry of the PS derivative of E2 with isolation and collisional activation of the m/z 272 ion resulted in steroid C and D ring cleavages analogous to those observed in electron ionization mass spectrometry. The product ion spectra of the PS derivatives of estrone, 17α-ethinylestradiol, equilin, and equilenin showed similar estrogen-specific ions. Using derivatization with PS chloride, we developed an LC-ESI-MS/MS method with multiple reaction monitoring of primary and confirmatory precursor-to-product ion transitions for the determination of E2 in serum.

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Section: Lc-esi-ms/ms Of the Ps Derivatives Of E1 Ee2 Eq And Eqnsupporting

confidence: 56%

Section: Lc-esi-ms/ms Of the Ps Derivatives Of E1 Ee2 Eq And Eqnmentioning

confidence: 78%

Section: Lc-es-ms 3 Of the Ps Derivative Of E2mentioning

confidence: 91%

“…4B). The base peak in the spectrum of the PS derivative of EE2 is at m/z 213, and is thought to arise from a D ring cleavage (Scheme 3) [38] as discussed above.…”

Section: Lc-esi-ms/ms Of the Ps Derivatives Of E1 Ee2 Eq And Eqnmentioning

confidence: 96%

Section: Lc-es-ms 3 Of the Ps Derivative Of E2mentioning

confidence: 99%

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Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Spink

2008

Analytical Biochemistry

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4′,17‐Dioxo‐5′H‐estra‐1(10),4‐dieno[3,2‐b]furan: Synthesis, Binding Affinity to the Estrogen Receptor, Uterotrophic and Antiimplantation Activities

Omar

Aboulwafa

Labouta

et al. 1996

Archiv der Pharmazie

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4',17-Dioxo-5'H-estra-1(10),4-dieno[3,2-b]furan (3) has been prepared by several routes starting from 2-bromoacetylestrone (2). Performance of the reaction with thiourea at elevated temperature provided compound 3 in good yield. When other reagents such as thiosemicarbazide, morpholine, sodium hydroxide or sodium hydride were treated with 2-bromoacetylestrone at room temperature, the furano derivative 3 was also obtained as the sole product. This new type of structural modification provided an estrogen nucleus deprived of the 3-hydroxyl function which was previously thought to be an essential requisite for binding to the estrogen receptor (ER). When evaluated in vitro for binding to the ER and in vivo for uterotrophic and antifertility activities, the furano derivative 3 was capable of inhibiting [3H]E2 binding by 16% while still eliciting high uterotrophic (99%) and postcoital antiimplantation (100%) activities relative to estradiol.

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Novel Steroidal 1,4‐Diketones and Pyridazine Derivatives as Potential Antiestrogens

Ismail

El-Tombary

Aboulwafa

et al. 1996

Archiv der Pharmazie

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A series of steroidal 1,4-diketone derivatives was synthesized by acid-catalyzed condensation of 2-acetylestradiol-17 beta-acetate with substituted phenylglyoxals. Conversion of the products into the corresponding pyridazine derivatives was achieved by reaction with hydrazine hydrate. The synthesized compounds were evaluated for their uterotrophic, antiuterotrophic, and antifertility activities in mature female albino rats. Among the compounds tested, the phenyl 2, p-bromophenyl 3, and p-methoxyphenyl 5 diketone derivatives displayed uterotrophic activity of 72%, 72%, and 91%, respectively. The gradation of antiestrogenic activity was assessed in vivo by the inhibition of the estrone-stimulated uterine growth. Compounds 2-5 showed moderate antiestrogenic activity of 53-56%. None of the tested compounds elicited antifertility activity as assessed by the post-coital antiimplantation activity test.

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Mass Spectrometry in Structural and Stereochemical Problems. XIV.¹ Steroids with One or Two Aromatic Rings²

Cited by 76 publications

References 0 publications

Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

Analysis of steroidal estrogens as pyridine-3-sulfonyl derivatives by liquid chromatography electrospray tandem mass spectrometry

4′,17‐Dioxo‐5′H‐estra‐1(10),4‐dieno[3,2‐b]furan: Synthesis, Binding Affinity to the Estrogen Receptor, Uterotrophic and Antiimplantation Activities

Novel Steroidal 1,4‐Diketones and Pyridazine Derivatives as Potential Antiestrogens

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