Antiandrogenic A-homo-B,19-dinor-analogues of androgens from 6β-chloro-5-methyl-19-nor-5β-androst-9-enes

1989 ◽  
Vol 54 (5) ◽  
pp. 1318-1326 ◽  
Author(s):  
Alexander Kasal
Keyword(s):  
Partial Hydrolysis ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Selective Acylation ◽  
Chloro Derivatives ◽  
Hydrolysis Of ◽  
Derivatives Of ◽  
Antiandrogenic Activity

6β-Chloro derivatives of 5-methyl-19-nor-5β-androst-9-enes (Westphalen diol type) with oxygen functionalities in positions 3 and 17 were converted into diene VI by treatment with lithium aluminium hydride. The lipophilic product of hydrogenation of VI was shown to be 4aα-methyl-A-homo-B,19-dinor-5β,10α-androstane-3β,17β-diol (IX). Various paths leading to dihydrotestosteron analogues, e.g. selective acylation or oxidation of diol IX and partial hydrolysis of diacetate X, have been realized. 17β-Hydroxy-4aα-methyl-A-homo-B,19-dinor-5β,10α-androstan-3-one (XVI) has been found to exhibit antiandrogenic activity.

The synthesis of Cyclododecane-r-1,c-5,c-9-triamine and r-1,c-5,c-9-Tris(2,3-dimethoxybenzamido)cyclododecane

1975 ◽  
Vol 28 (3) ◽  
pp. 673 ◽  
Author(s):  
DJ Collins ◽  
C Lewis ◽  
JM Swan
Keyword(s):  
Aqueous Solution ◽  
Acid Hydrolysis ◽  
Sulphuric Acid ◽  
Sodium Carbonate ◽  
Sodium Azide ◽  
Room Temperature ◽  
Dimethyl Formamide ◽  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Hydrolysis Of

Treatment of cyclododecane-r-1,c-5,c-9-triyl tris(p-toluenesulphonate) with sodium azide in dimethyl-formamide at 100� for 6 h gave the corresponding cis,cis-triazide which upon hydrogenation or reduction with lithium aluminium hydride gave cyclododecane-r-1,c-5,c-9-triamine, isolated as the tris-salicylidene derivative. Acid hydrolysis of this, removal of the salicylaldehyde, and treatment of the aqueous solution with sodium carbonate and 2,3-dimethoxybenzoyl chloride gave r-1,c-5,c- 9-tris(2,3-dimethoxybenzamido)cyclododecane. ��� Treatment of (E,E,E)-cyclododeca-1,5,9-triene with an excess of acetonitrile and sulphuric acid at room temperature for three days gave 18% of (E,E)-1-acetamidocyclododeca-4,8-diene; no di- or tri-amides were isolated.

O-Benzylidene Derivatives of D-Arabinose Diethyl and Dipropyl Dithioacetal

1996 ◽  
Vol 49 (3) ◽  
pp. 273 ◽  
Author(s):  
J Kuszmann ◽  
E Gacsbaitz
Keyword(s):  
Hydrochloric Acid ◽  
Zinc Chloride ◽  
Partial Hydrolysis ◽  
Kinetic Control ◽  
Toluenesulfonic Acid ◽  
Thermodynamic Phase ◽  
Hydrolysis Of ◽  
Derivatives Of

Benzylidenation of D-arabinose diethyl and dipropyl dithioacetals with α,α-dimethoxytoluene in the presence of p-toluenesulfonic acid has been studied in detail. Under kinetic control the two terminal dioxolan -type 4,5-O-(R)- and 4,5-O-(S)-benzylidene diastereomers are formed first which are in equilibrium with each other In the thermodynamic phase of the reaction the corresponding dioxan -type 3,5-O-(R)- benzylidene isomer is formed too, but all three monobenzylidene isomers are gradually converted into the four possible dioxolan -type 2,3 : 4,5-di-O benzylidene diastereomers . The dioxan -type 2,4:3,5-di-O-benzylidene isomer was present only in trace amounts. When benzaldehyde was used as reagent in the presence of hydrochloric acid or zinc chloride only the 2,3: 4,5-di-O-benzylidene diastereomers were formed. Partial hydrolysis of the dibenzylidene derivatives yielded the corresponding 2,3-O-benzylidene diastereomers. Structures, including the chirality of the benzylidene groups, were determined by n.m.r. spectroscopy. A mechanism suggested for the reaction was partially supported by equilibration studies.

4,5-Seco-4,6-cyclosteroids. III. Observations on the course of reductive rearrangement of 6β-Bromo-4β,5-epoxy-5β-cholestan-3β-ol

1969 ◽  
Vol 22 (4) ◽  
pp. 807 ◽  
Author(s):  
DJ Collins ◽  
JJ Hobbs ◽  
RJ Rawson
Keyword(s):  
Hydrogen Bromide ◽  
High Yield ◽  
Lithium Aluminium Hydride ◽  
Experimental Conditions ◽  
Lithium Aluminium ◽  
Reaction Proceeds ◽  
Derivatives Of

It has been shown that reductive rearrangement of 6β-bromo-4β,5-epoxy- 5β-cholestan-3β-ol (I) to 4,5-seco-4,6-cycle-6β-cholestane-3β,5α-diol (IXa) with lithium aluminium hydride in tetrahydrofuran proceeds via 6β-bromo-5β-cholestane-3β,5-diol (IIa). Relevant reactions of the latter and the corresponding 3-ketone are discussed. ��� Similar conversion of the 3-epimer of (I) into 4,5-seco-4,6-cyclo- 6β-cholestane-3α,5α-diol (XIIIa) in high yield indicates that reductive rearrangement of the 6β-bromo-5β-hydroxy moiety proceeds without participation of the 3-aluminate complex. Some derivatives of (XIIIa) are described. ��� Experimental conditions required for the conversion of (I) into (IXa) are defined. ��� Combined evidence indicates that the reaction proceeds in a concerted manner by essentially base-catalysed, 1,3-elimination of hydrogen bromide from diol (IIa) with 4,5-bond migration to give the formal intermediate 3β-hydroxy-4,5-seco-4,6-cyclo-6β-cholestan-5-one (VI), further reduced to (IXa).

Hydrolytic products of 4-aryl-2,3-dicyano-1-naphthol derivatives

1981 ◽  
Vol 46 (9) ◽  
pp. 2207-2216 ◽  
Author(s):  
Jiří Křepelka ◽  
Iva Vančurová ◽  
Jiří Holubek ◽  
Jiří Roubík
Keyword(s):  
Dicarboxylic Acids ◽  
Ring Closure ◽  
Partial Hydrolysis ◽  
H Nmr ◽  
Antiviral Effects ◽  
Hydrolysis Of ◽  
Derivatives Of ◽  
Naphthol Derivatives ◽  
Intramolecular Ring

Depending on the conditions of hydrolysis, vicinal aromatic dicyano derivatives Ia-Ic gave anhydrides IIa-IIe and imides of 4-aryl-1-alkoxynaphthalene-2,3-dicarboxylic acids, IIIa,b, along with products of partial hydrolysis, decarboxylation and demethylation, IVa-IVd, IVf-IVg, and derivatives of benzo(c)fluorene, Va-Vc. The derivatives Va-Vc were also obtained by acid hydrolysis of dicyano derivatives Id-Ig. Methanolysis of the anhydride IId gave a mixture of positional isomers, IVh, which was esterified to the diester IVe. Intramolecular ring closure of the isomers IVh afforded derivatives of benzo(c)fluorene, VIa-VIb. The structures of the selected compounds were corroborated by IR and 1H NMR spectra. The compounds Va-Vc exhibited antiviral effects and interferonogenic activities in vivo.

Partial hydrolysis of acyl 1,6-anhydro-β-D-glucopyranose

1984 ◽  
Vol 49 (8) ◽  
pp. 1780-1787 ◽  
Author(s):  
Štefan Kučár ◽  
Juraj Zámocký ◽  
Juraj Zemek ◽  
Dušan Anderle ◽  
Mária Matulová
Keyword(s):  
Acid Hydrolysis ◽  
Hydrazine Hydrate ◽  
Hydrogen Chloride ◽  
Ester Group ◽  
The Other ◽  
Hydroxyl Group ◽  
Partial Hydrolysis ◽  
Substantial Influence ◽  
Hydrolysis Of ◽  
Derivatives Of

Partial hydrolysis of per-O-acetyl- and per-O-benzoyl derivatives of 1,6-anhydro-β-D-glucopyranose with methanolic hydrogen chloride and hydrazine hydrate was investigated. The acyl group at C(3) is of substantial influence on the course of hydrolysis. The esterified hydroxyl group at C(3) was found to be most stable on acid hydrolysis with methanolic hydrogen chloride when compared with that at C(2), or C(4); on the other hand, this ester group is the most labile upon hydrolysis with hydrazine hydrate. Selectivity of the respective ester groups towards hydrolysis made it possible to prepare all variations of acetyl and benzoyl derivatives of 1,6-anhydro-β-D-glucopyranose.

Synthesis of mono- and di-functional benzyl and phenethyl derivatives containing silicon

1967 ◽  
Vol 45 (17) ◽  
pp. 1957-1961 ◽  
Author(s):  
Avner Rotman ◽  
David Gertner ◽  
Albert Zilkha
Keyword(s):  
Lithium Aluminium Hydride ◽  
Lithium Aluminium ◽  
Hydrolysis Of

Dimethylbis(p-tolyl)silane was converted into the mono- or di-benzyl bromides by reaction with appropriate equivalents of N-bromosuccinimide; these were then converted into the nitriles, which were hydrolyzed to the corresponding phenylacetic acids or reduced to the phenethylamines. The mono- and di-phenethyl alcohols were prepared by reduction of the corresponding acids with lithium aluminium hydride. The dialdehyde, dimethylbis(p-formylphenyl)silane, was prepared by hydrolysis of dimethylbis(p-dibromomethylphenyl)silane.

scholarly journals Synthesis of olivomycose (2,6-dideoxy-3-C-methyl-L-arabino-hexose)

1969 ◽  
Vol 47 (23) ◽  
pp. 4467-4471 ◽  
Author(s):  
E. H. Williams ◽  
W. A. Szarek ◽  
J. K. N. Jones
Keyword(s):  
Wittig Reaction ◽  
High Yield ◽  
Lithium Aluminium Hydride ◽  
Ruthenium Tetroxide ◽  
Lithium Aluminium ◽  
Acid Catalyzed ◽  
Hydrolysis Of

Oxidation of methyl 4,6–O-benzylidene-2-deoxy-α-L-arabino-hexopyranoside (1) with ruthenium tetroxide gave the 3-ketone 2 in high yield. A Wittig reaction between methylenetriphenylphosphorane and compound 2 gave methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methylene-α-L-erythro-hexopyranoside (3), which was hydrated by the oxymercuration–demercuration procedure to afford methyl 4,6-O-benzylidene-2-deoxy-3-C-methyl-α-L-arabino-hexopyranoside (4). The reaction of compound 4 with N-bromosuccinimide gave methyl 4-O-benzoyl-6-bromo-2,6-dideoxy-3-C-methyl-α-L-arabino-hexopyranoside (5) in high yield. Treatment of compound 5 with lithium aluminium hydride followed by acid-catalyzed hydrolysis of the resultant product, gave L-olivomycose (6).

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