Synthesis, X-ray Crystal Structure and Antiestrogenic Activity of 17-Methyl-16,17-secoestra-1,3,5(10)-triene Derivatives

2005 ◽  
Vol 70 (1) ◽  
pp. 63-71 ◽  
Author(s):  
Marija N. Sakač ◽  
Dušan A. Miljković ◽  
Katarina M. Penov Gaši ◽  
Mirjana Popsavin ◽  
Olivera R. Klisurić ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Structural Analysis ◽  
Sodium Borohydride ◽  
Catalytic Hydrogenation ◽  
Chiral Center ◽  
Reaction Conditions ◽  
X Ray ◽  
Antiestrogenic Activity ◽  
Biological Tests

Starting from 3-(benzyloxy)-16-(hydroxyimino)-estra-1,3,5(10)-trien-17-one (1) several 17-methyl-16,17-secoestratriene derivatives were synthesized. In the first step of synthesis, hydroxyimino ketone 1 was transformed into 3-(benzyloxy)-16-(hydroxyimino)-17α-methylestra-1,3,5(10)-trien-17β-ol (2), the Beckmann fragmentation of which gave 3-(benzyloxy)-17-methyl-17-oxo-16,17-secoestra-1,3,5(10)-triene-16-nitrile (3a). Reduction of 3a with sodium borohydride yielded (17S)-3-(benzyloxy)-17-hydroxy-17-methyl-16,17-secoestra-1,3,5(10)-triene-16-nitrile (4a), whose configuration at the newly formed chiral center was established by X-ray structural analysis. Catalytic hydrogenation of compound 3a under different reaction conditions yielded 3-hydroxy-17-methyl-17-oxo-16,17-secoestra-1,3,5(10)-triene-16-nitrile (3b) and 16-amino-17-methyl-16,17-secoestra-1,3,5(10)-triene-3,17-diol (6b). Biological tests in vivo of compounds 3b and 6b showed their moderate antiestrogenic activity.

Synthesis and Estrogenic Activity Screening of Some 6,9-Disubstituted Estradiol Derivatives

2005 ◽  
Vol 70 (4) ◽  
pp. 479-486 ◽  
Author(s):  
Marija N. Sakač ◽  
Katarina M. Penov Gaši ◽  
Mirjana Popsavin ◽  
Evgenija A. Djurendić ◽  
Silvana Andrić ◽  
...  
Keyword(s):  
Acetic Anhydride ◽  
Sodium Borohydride ◽  
Thionyl Chloride ◽  
Estrogenic Activity ◽  
Chromium Vi ◽  
Antiestrogenic Activity ◽  
Estradiol Derivatives ◽  
Biological Tests ◽  
Activity Screening

Oxidation of estradiol dipropionate (1) with chromium(VI) oxide-3,5-dimethylpyrazole complex yielded 9α-hydroxy-6-oxoestra-1,3,5(10)-triene-3,17β-diyl dipropionate (2) and 6-oxoestra-1,3,5(10)-triene-3,17β-diyl dipropionate (3). Dehydration of compound 2 with phosphorus(V) oxide or acetic anhydride gave 6-oxoestra-1,3,5(10),9(11)-tetraene-3,17β-diyl dipropionate (5). Reduction of compounds 2 and 5 with sodium borohydride afforded 3,6β,9α-trihydroxyestra-1,3,5(10)-triene-17β-yl propionate (4) and 3,6β-dihydroxyestra-1,3,5(10),9(11)-tetraene-17β-yl propionate (6), respectively. The action of thionyl chloride on compound 2 yielded 6-hydroxyestra-1,3,5(10),6,8-pentaene-3,17β-diyl dipropionate (7). Biological tests in vivo of these compounds showed a moderate antiestrogenic activity of compound 4.

Effects of dietary alteration of bicarbonate and magnesium on rat bone

1986 ◽  
Vol 250 (2) ◽  
pp. F302-F307 ◽  
Author(s):  
J. M. Burnell ◽  
C. Liu ◽  
A. G. Miller ◽  
E. Teubner
Keyword(s):  
Crystal Structure ◽  
Bone Formation ◽  
X Ray Diffraction ◽  
X Ray ◽  
Growing Rats ◽  
Final Composition ◽  
Rat Bone

To study the effects of bicarbonate and magnesium on bone, mild acidosis and/or hypermagnesemia were produced in growing rats by feeding ammonium chloride and/or magnesium sulfate. Bone composition, quantitative histomorphometry, and mineral x-ray diffraction (XRD) characteristics were measured after 6 wk of treatment. The results demonstrated that both acidosis (decreased HCO3) and hypermagnesemia inhibited periosteal bone formation, and, when combined, results were summative; and the previously observed in vitro role of HCO3- and Mg2+ as inhibitors of crystal growth were confirmed in vivo. XRD measurements demonstrated that decreased plasma HCO3 resulted in larger crystals and increased Mg resulted in smaller crystals. However, the combined XRD effects of acidosis and hypermagnesemia resembled acidosis alone. It is postulated that the final composition and crystal structure of bone are strongly influenced by HCO3- and Mg2+, and the effects are mediated by the combined influence on both osteoblastic bone formation and the growth of hydroxyapatite.

The Meisenheimer rearrangement in heterocyclic synthesis. II. Synthesis and X-ray crystal structure of a tetrahydro-1H-2,3-benzoxazocine and preparation of a hexahydro-2,3-benzoxazonine

1980 ◽  
Vol 33 (6) ◽  
pp. 1323 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
PE Davies ◽  
CLWAH Raston
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Acetic Acid ◽  
Crystal And Molecular Structure ◽  
Phosphorus Oxychloride ◽  
Crystallographic Analysis ◽  
Heterocyclic Synthesis ◽  
Reaction Conditions ◽  
X Ray ◽  
Heterocyclic Derivatives

The heterocyclic derivatives, 8,9-dimethoxy-3-methyl-1-phenyl-3,4,5,6- tetrahydro-1H-2,3-benzoxazocine(3a) and 9,10-dimethoxy-3-methyl-1- phenyl-1,3,4,5,6,7-hexahydro-2,3-benzoxazonine (3b),examples of two new ring systems, have been prepared by Meisenheimer rearrangement of the corresponding 2-benzazepine and 2-benzazocine N-oxide derivatives (2a) and (2b). The Bischler-Napieralski-type cyclization reaction was used in the preparation of the tertiary amine precursors of these N-oxides reaction conditions for the cyclization were critical and phosphorus oxychloride in refluxing butanenitrile was found to give the best yields of the seven- or eight-membered cyclic imine intermediates. Reductive cleavage of the benzoxazocine derivative (3a) with zinc in acetic acid followed by N-methylation gave the expected product, [2-{3- (dimethylamino)propyl}-4,5-di-methoxyphenyl]phenylmethanol (12). The crystal and molecular structure of (3a) has been determined by X-ray crystallographic analysis.

The synthesis, molecular and crystal structure of the 1:1 adduct of triphenyltin chloride with 2,3-diphenylthiazolidin-4-one

1995 ◽  
Vol 73 (1) ◽  
pp. 95-99 ◽  
Author(s):  
Frank E. Smith ◽  
Rosemary C. Hynes ◽  
John Tierney ◽  
Ying Z. Zhang ◽  
George Eng
Keyword(s):  
Crystal Structure ◽  
Structural Analysis ◽  
Oxygen Atom ◽  
Dutch Elm Disease ◽  
Monoclinic Space Group ◽  
Monodentate Ligand ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Triphenyltin Chloride ◽  
Mössbauer Data

The title compound was synthesized as part of an effort to produce a more effective fungicide to combat Dutch Elm Disease (DED), which is caused by the fungus Ceratocystisulmi. A full X-ray structural analysis of the 1:1 adduct has been carried out and the results are reported along with the Mössbauer data for the compound. The crystals are monoclinic, space group P21/a with a = 19.240(3) Å, b = 9.1463(24) Å, c = 19.3512(24) Å, β = 118.874(8)°, V = 2982.0(10) Å3, z = 4, and Dcalc = 1.427 Mg m−3. The final discrepancy factors are RF = 0.056 and Rw = 0.058 for 1915 significant reflections. The QS and IS values in the Mössbauer spectrum of the complex are 3.08 mm s−1 and 1.28 mm s−1, respectively. The 2,3-diphenylthiazolidin-4-one behaves as a monodentate ligand and coordinates to the tin through the oxygen atom. The complex exhibits a trigonal bipyramidal configuration with the three phenyl groups in equatorial positions and the chloride and ligand oxygen occupying the apical sites. Keywords: triorganotin, fungicide, Dutch Elm Disease, thiazolidin-4-one.

Cyano-Bridged Bimetallic Complexes of Copper(II) with Nitroprusside. Crystal Structure of [Cu(H2NCH2CH(NH2)CH3)2Fe(CN)5NO] . H2O

2000 ◽  
Vol 53 (3) ◽  
pp. 225 ◽  
Author(s):  
Zdenek Smékal ◽  
Zdenek Trávnícek ◽  
Jaromír Marek ◽  
Milan Nádvornik
Keyword(s):  
Crystal Structure ◽  
Structural Analysis ◽  
Magnetic Measurements ◽  
X Ray ◽  
Cyanide Group ◽  
Cyanide Ligand ◽  
Binuclear Structure ◽  
Tetragonal Pyramidal ◽  
Cyanide Ligands ◽  
Diamine Ligands

Five new complexes of compositions [Cu(1,2-pn)2Fe(CN)5NO]·H2O (1,2-pn = propane-1,2-diamine) and [Cu(L)Fe(CN)5NO]·xH2O (L = tmen (N,N,N′,N′-tetramethylethane-1,2-diamine), x = 0.5; L = trimeen (N,N,N′-trimethylethane-1,2-diamine), x = 1; L = dien (N-(2-aminoethyl)ethane-1,2-diamine), x = 0; L = medpt (N-(3-aminopropyl)-N-methylpropane-1,3-diamine), x = 2) have been isolated from the reaction mixture of Cu(ClO4)2·6H2O (or CuCl2·2H2O), the amine and Na2 [Fe(CN)5NO]·2H2O in water. The complexes have been characterized by infrared and ultraviolet–visible spectroscopies, and magnetic measurements. Single-crystal X-ray structural analysis revealed that the [Cu(1,2-pn)2Fe(CN)5NO]·H2O complex assumes a cyanide-bridged binuclear structure in which iron(II) is six-coordinated by five cyanide ligands and one nitrosyl group (the nitrosyl group lies cis to the bridging cyanide group), while copper(II) is five-coordinated by two propane-1,2-diamine ligands and a bridging cyanide ligand in a distorted tetragonal pyramidal arrangement.

scholarly journals Unusual formation of (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]azepin-5(7H)-one and its crystal structure

2017 ◽  
Vol 73 (10) ◽  
pp. 1497-1500
Author(s):  
Khamid U. Khodjaniyazov ◽  
Utkir S. Makhmudov ◽  
Kambarali K. Turgunov ◽  
Burkhon Z. Elmuradov
Keyword(s):  
Crystal Structure ◽  
Structural Analysis ◽  
Aqueous Ammonia ◽  
Boat Conformation ◽  
X Ray ◽  
First Time ◽  
Twist Boat ◽  
Unusual Formation

Selective C-formylation of 8,9,10,11-tetrahydropyrido[2′,3′:4,5]pyrimido[1,2-a]-azepin-5(7H)-one has been studied for the first time. It was revealed that formylation proceeds by the formation of an intermediate salt, which due to the re-amination process on treatment with aqueous ammonia transformed into the corresponding (E)-11-(aminomethylene)-8,9,10,11-tetrahydropyrido[2′,3′:4,5]-pyrimido[1,2-a]azepin-5(7H)-one, C13H14N4O, as anE-isomer. Formylation was carried out by Vilsmeier–Haack reagent and the structure of the synthesized compound was confirmed by X-ray structural analysis, spectroscopic and LC–MS methods. In the molecule, the seven-membered pentamethylene ring adopts a twist-boat conformation.

scholarly journals Crystal structure of a pyridoxal 5′-phosphate-dependent aspartate racemase derived from the bivalve mollusc Scapharca broughtonii

2017 ◽  
Vol 73 (12) ◽  
pp. 651-656 ◽  
Author(s):  
Taichi Mizobuchi ◽  
Risako Nonaka ◽  
Motoki Yoshimura ◽  
Katsumasa Abe ◽  
Shouji Takahashi ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Binding Site ◽  
Active Site ◽  
Metal Binding ◽  
Bivalve Mollusc ◽  
Active Site Residues ◽  
X Ray ◽  
Aspartate Racemase ◽  
Scapharca Broughtonii

Aspartate racemase (AspR) is a pyridoxal 5′-phosphate (PLP)-dependent enzyme that is responsible for D-aspartate biosynthesis in vivo. To the best of our knowledge, this is the first study to report an X-ray crystal structure of a PLP-dependent AspR, which was resolved at 1.90 Å resolution. The AspR derived from the bivalve mollusc Scapharca broughtonii (SbAspR) is a type II PLP-dependent enzyme that is similar to serine racemase (SR) in that SbAspR catalyzes both racemization and dehydration. Structural comparison of SbAspR and SR shows a similar arrangement of the active-site residues and nucleotide-binding site, but a different orientation of the metal-binding site. Superposition of the structures of SbAspR and of rat SR bound to the inhibitor malonate reveals that Arg140 recognizes the β-carboxyl group of the substrate aspartate in SbAspR. It is hypothesized that the aromatic proline interaction between the domains, which favours the closed form of SbAspR, influences the arrangement of Arg140 at the active site.

Synthesis and1H NMR Structural Analysis of 11-Aryl/Heteroarylnaphtho[2,1-b]furans: X-Ray Crystal Structure of 11-(4′-Pyridyl)naphtho[2,1-b]furan.

ChemInform ◽  
2005 ◽  
Vol 36 (47) ◽  
Author(s):  
Sabir H. Mashraqui ◽  
Mamta B. Patil ◽  
Yogesh Sangvikar ◽  
Mohamed Ashraf ◽  
Hitesh D. Mistry ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Structural Analysis ◽  
X Ray

scholarly journals Derivatives of the triaminoguanidinium ion, 5. Acylation of triaminoguanidines leading to symmetrical tris(acylamino)guanidines and mesoionic 1,2,4-triazolium-3-aminides

2017 ◽  
Vol 13 ◽  
pp. 579-588 ◽  
Author(s):  
Jan Szabo ◽  
Julian Greiner ◽  
Gerhard Maas
Keyword(s):  
Crystal Structure ◽  
Carboxylic Acid ◽  
Nitrogen Atom ◽  
Catalytic Hydrogenation ◽  
Acid Chlorides ◽  
Reaction Conditions ◽  
Derivatives Of ◽  
Guanidinium Salts ◽  
Triazolium Salts

Depending on the reaction conditions, N,N’,N’’-tris(benzylamino)guanidinium salts can react with carboxylic acid chlorides to form either symmetrical N,N’,N’’-tris(N-acyl-N-benzylamido)guanidines 6 or mesoionic 4-amino-1,2,4-triazolium-3-hydrazinides 7. The latter were converted into 1,2,4-triazolium salts by protonation or methylation at the hydrazinide nitrogen atom. Neutral 1,2,4-triazoles 10 were obtained by catalytic hydrogenation of an N-benzyl derivative. Crystal structure analyses of a 4-benzylamino-1,2,4-triazolium-3-hydrazinide and of two derived 1,2,4-triazolium salts are presented.

Kristall- und Molekülstruktur von 5.10-Dihydro-5.10-diniethylphenaziniiimtniodid und 5.10-Dihydro-5.10-diethylphenaziniumtriiodid / Molecular and Crystal Structure of 5,10-Dihydro-5.10-dimethylphenaziniumtriiodide and 5.10-Dihydro-5.10-diethylphenazinium triiodide

1978 ◽  
Vol 33 (8) ◽  
pp. 838-842 ◽  
Author(s):  
H. J. Keller ◽  
W. Moroni ◽  
D. Nöthe ◽  
M. Scherz ◽  
J. Weiss
Keyword(s):  
Crystal Structure ◽  
Radical Cations ◽  
Unit Cell ◽  
Lattice Parameters ◽  
Molecular And Crystal Structure ◽  
Reaction Conditions ◽  
Space Group ◽  
X Ray ◽  
R Value

Oxidation of 5,10-dihydro-5,10-dimethylphenazine and 5,10-dihydro-5,10-diethyl-phenazine under different reaction conditions leads to several iodine containing solids. The preparation and X-ray structure of two of them, 5,10-dihydro-5,10-dimethyl-phcnaziniumtriiodide (3) and 5,10-dihydro-5,10-diethylphenaziniumtriiodido (4) are reported here.Compound 3 crystallizes in space group P21/n with lattice parameters a = 8.552(6) Å, b= 16.953(2) Å, c- 12.157(9) Å and β= 103.46(2)° with four formula units in the unit cell. The structure was refined to an R-value of 0.046 using 2387 independent reflections. The lattice constains distinct, slightly distorted triiodide ions and bent 5,10-dihydro-5,10-dimethylphenazinium radical cations. Compound 4 crystallizes in the same space group P21/n with lattice parameters a = 8.531(6) Å, b = 8.332(21) Å, c = 13.320(15) Å and β= 94.44(19)° with two formula units in the unit cell. The structure was refined to an R-value of 0.076 using 1195 independent reflections. The lattice contains strictly linear symmetrical triiodide ions and planar centrosymmetrical 5,10-dihydro-5,10-diethyl- phenazinium radical cations.

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