19-nortestosterone acetate

A solution of 1 g of the diacetate (III) in 100 cc of n-heptane containing 2.5 cc of cyclopentanol and 50 mg of p-toluenesulfonic acid is heated under reflux for 20 hours. After cooling, a few drops of pyridine are added and the solvent is eliminated by evaporation under vacuum. The residue is taken up with methanol to give 3-cyclopentyl enolether of 17a-ethynyl-19-nortestosterone acetate which, after recrystallization from methanol, melts at 182°C to 184°C. 

During the period of time when the nature of the 19-nortestosterone acetate-dependent photoinactivation was under investigation, a new bacterial steroid isomerase was obtained from extracts of Pseudomonas putida (Biotype B) in nearly homogeneous form and some of its physical and enzymatic properties were characterized (64, 65, 66). The putida isomerase is similar in its molecular weight and quaternary structure to the testosteroni isomerase. Chemically, the most striking difference between the two isomerases is the presence of four residues of cysteine per polypeptide chain of the putida isomerase whereas no cysteine or cystine is present in the testosteroni isomerase. N-Terminal sequence analysis of the putida isomerase demonstrated substantial sequence homology between the two enzymes. 

Oxidation of the 3,5-enol chloride of 19-nortestosterone acetate with t-butyl chromate followed by catalytic reduction provides an alternative route to 17j -acetoxyoestr-5-en-7-one and nitration of the 3,5-enol ether with tetranitro-... 

Nortestosterone acetate Active site of A -3-ketosteroid iso-merase Photoattachment and enzyme inactivation 128... 

Reaction mixtures contained 5 itM isomerase, 3.3% ethanol, and 0.04 M sodium phosphate, pH 7.0, plus additions. The concentrations of the additions were cyclohexenone, 330 iiM-, testosterone, 23 nM-, 19-nortestosterone, 24 nM-, 19-nortestosterone acetate, 21 iiM. Final volumes were 0.15 ml. Irradiations were performed using the old apparatus (see text). 

Chemical changes accompanying the 19-nortestosterone acetate-promoted photoinactivation were monitored by amino acid analysis. It was observed that both aspartic acid and histidine decreased with increasing extent of inactivation. In two kinetic studies comparing the rates of activity, aspartic acid and histidine losses, it was observed that the first-order rate constants for activity loss and loss of one residue of aspartate (asparagine) were nearly the same (fcactivity = -0.54 hr- -0.55 hr ... 

The presence of oxygen was found to markedly influence the character of the photochemical events occurring during photoinactivation promoted by 19-nortestosterone acetate. Oxygen inhibited both the loss of activity and the destruction of aspartate whereas it stimulated destruction of histidine. Under anaerobic conditions, no significant loss of histidine occurred whereas 0.98 of 12 moles of aspartate (per mole of enzyme monomer, MW 13,394) was destroyed and 85% of the activity was lost. 

Norbiotinyl p-nitrophenyl ester, 615 Norepinephrine, 336, 591, 592 Norelevorphanol, synthesis of, 605 19-Nortestosterone, 476 19-Nortestosterone acetate, 89, 476-478 Nuclear-cytoplasmic interactions, 644 Nucleases, 175, 368-362... 

With 2537 k-Light. 1 g (140) in 140 ml anhydrous dioxane is irradiated for 20 hr at room temperature with a Hanau NK 6/20 low-pressure mercury lamp placed in a central water-cooled quartz finger. 0.19 g of (141) crystallize from the crude reaction mixture as described above. Chromatography of the residual material on silica gel with benzene-ethyl acetate (4 1) gives 0.29 g of B-nortestosterone acetate [(142) 28.5 %] and starting material (140). 

Norsteroids via 19-nitriles, 268 A-N ortestosterone, 410 B-nortestosterone, 430 D-nortestosterone, 441 19-Nortestosterone, 282, 321 B-nortestosterone acetate, 324, 329... 

Hydrolysis of the acetate (71) followed by Oppenauer oxidation gives B-norcholest-4-en-3-one in high yield. An analogous reaction sequence can be used to prepare B-norprogesterone and derivatives of B-nortestosterone from pregnenolone acetate and dehydroepiandrosterone acetate, respectively."" ... 

Reduction of 19-nortestosterone (23) with sodium borohydride leads to a mixture of isomers consisting largely of the 3p-alcohol (24) the lack of stereospecificity can be traced back to the relative remoteness of that 3-position from chiral centers which could direct the incoming reagent. Acylation of diol 24 with acetic anhydride in the presence of... 

The presence of a 7a-methyl group has been found to potentiate anabolic activity. Acetylation of 19-nortestosterone affords the corresponding 17-acetate... 

Methyl 3a,6a-dihydroxycholanate, 240 1-Methylestrone 3-methyl ether, 10, 27 4b/3-Methyl-7-ethylenedioxy-1,2,3,4, 4a ,4b/3,5,6,7,8,10,1 Oaa-dodecahydro-phenanthrene-1 /3,4/3-diol, 236 14C-Methyl iodide, 211 ds-Methyl iodide, 210, 214 Methyl lithocholate tosylate, 329 1-Methyl-19-nortestosterone, 27 6a-Methylprednisolone, 410 6a-Methylprednisolone BMD, 410 16/3-Methylprednisone, 87 18-Methylpregn-4-ene-3/3,17a,20f-triol, 243 20-Methylpregn-5-en-3/3-ol, 415 17a-Methylpregnenolone acetate, 48 17a-Methyltestosterone, 438 16/3-Methyl- 11a,17a,21 -trihydroxy- 5 /3-pregnane-3,20-dione 21-acetate, 299, 300 20-Methyl-3/3-trityloxypregn-5-ene, 415 3/3-Methoxycholestane, 136 1-Methoxycyclohexene, 18 3-Methoxyestra-3,5(10)-diene, 18, 27... 

Many studies have shown that lactation is not adversely affected by depot medroxyprogesterone acetate and that breast-milk production may even be increased (35). Because of the low binding affinity of medroxyprogesterone to sex hormone binding globulin, the concentration of steroids in the milk is close to that in the maternal plasma, unlike the 19-nortestosterone derivatives. 

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