Improved synthesis of 16alpha-hydroxylated androgens: intermediates of estriol formation in pregnancy.

16alpha-Hydroxyandrostenedione (16alpha-hydroxyandrost-4-ene-3,17-dione), 16alpha-hydroxytestosterone (16alpha,17beta-dihydroxyandrost-4-en-3-one) and 16alpha-hydroxydehydroepiandrosterone 3-sulfate (3beta, 16alpha-dihydroxyandrost-5-en-17-one 3-monosulfate) were synthesized by a new chemical approach with much improved yield. 16alpha-Bromoandrostendione was converted to the hydrazone of 16alpha-hydroxyandrostenedione which gave 16alpha-hydroxyandrostenedione on acid hydrolysis in total 63% yield. Oxidation of 16alpha-hydroxydehydroepiandrosterone with Jones' reagent also selectively afforded 16alpha-hydroxyandrostenedione. 16alpha-Hydroxytestosterone was observed by selective reduction of 16alpha-hydroxyandrostenedione with sodium borohydride. Reaction of 16alpha-hydroxydehydroepiandrosterone with chlorosulfonic acid in pyridine selectively gave the 3-monosulfate. The structure of the sulfate was deduced from its solvolysis to the starting material, and its acetylation and subsequent solvolysis to 16alpha-hydroxydehydroepiandrosterone 16-acetate. All procedures are suitable for large scale synthesis without the use of microorganisms.     

Depsidone constituents from the quintaria group of Nephroma species

A new lichen depsidone was isolated, in the form of its triacetate derivative from the acetylated extracts of Nephroma antarcticum and has been demonstrated to be hypoconstictic acid-triacetate. Two related depsidones, hypostictic acid hyposalazinic acid, were isolated from N. australe.     

Stabilization of rat liver lysosomes by new anti-inflammatory steroids in vitro

Steroid acid esters, synthesized by modifying the 17-ketol side chain of prednisolone, were tested for their in vitro ability to stabilize heavy mitochondrial lysosomes prepared from rat liver. Membrane stabilization was determined by assessing capability of steroids to decrease extrusion of the marker enzymes (acid phosphatase, beta-glucuronidase and aryl sulfatase) from lysosomes incubated in hypo-osmotic sucrose-Tris acetate buffer. Results indicated that prednisolone (1) significantly inhibited the lysosomal release of acid phosphatase as did the new anti-inflammatory steroid, methyl 20-dihydroprednisolonate. Methyl prednisolonate exhibited weak membrane stabilization capacities and 20-dihydroprednisolonic acid, a metabolic product of methyl 20-dihydroprednisolonate, showed virtually no membrane stabilization.     

Biosynthesis of triterpenoids from amino acids in Pisum sativum. The distribution of the radioactivity in squalene biosynthesized from radioisotopically labelled l-leucine and l-valine

Radioisotopically labelled l-leucine and l-valine were fed to Pisum sativum and incorporated into squalene and β-amyrin. Chemical degradation of the radioactive squalene revealed an equal distribution of the radioactivity in the isopentenyl pyrophosphate(IPP)-derived and the 3,3-dimethylallyl pyrophosphate(DMAPP)-derived moieties of the squalene molecule, unlike the unbalanced distribution in favour of the DMAPP-derived moiety of a monoterpenoid molecule biosynthesized from these amino acids by higher plants.     

DDT inhibition of Ca-Mg ATPase from peripheral nerves and muscles of lobster, Homarus americanus

Sensitivity of CaMg ATPase from axonic plasma membrane (APM) and sarcoplasmic reticulum (SR) of lobster, $\text{Homarus}\text{,}\text{americanus}$, to DDT was studied. The CaMg ATPase found in SR with the high Ca²⁺ affinity is sensitive to DDT while the portion of ATPase related to the low Ca²⁺ affinity site is not inhibited by DDT. Also, DDT is more inhibitory against the CaMg ATPase prepared from APM than the one obtained from SR. The relationship between inhibition of the CaMg ATPase by DDT in the axonic nerve membrane and $\text{in}\text{,}\text{vivo}$ poisoning symptoms of the nervous system is discussed.     

Biosynthesis of sesquiterpenes in Hymenaea inferred from their quantitative co-occurrence

Leaf pocket resins of 11 species of the tropical arborescent genus Hymenaea are virtually identical qualitatively, but of widely varying quantitative proportions. Within this large range of variability, several strong positive quantitative correlations between resin constituents were found, especially between caryophyllene and β-humulene and between γ-muurolene and δ-cadinene. These data lead to clarification of sesquiterpene biosynthetic routes in Hymenaea. In addition, quantitative relationships found among caryophyllene, α- and β-selinene, γ-muurolene and δ-cadinene are explained only with difficulty by long accepted biosynthetic pathways, and the intermediacy of germacrenes is suggested.     

β-Ionon und patchoulialkohol aus den unterirdischen teilen von Valeriana officinalis

l-(+)-Bornesitol was detected in 23 of 33 genera of Gentianaceae investigated. The only subtribe without l-(+)-bornesitol (3 species tested) was Exacinae. None of the five genera of Menyanthaceae examined were found to contain l-(+)-bornesitol.     

Resolution of cyclic AMP stimulated protein kinase from polymerization-purified brain microtubules.

Polymerization-deploymerization purified microtubules from mouse brain contain, in addition to tubulin, several minor proteins, including protein kinase activity. The protein kinase copurifies with microtubules in constant proportion to tubulin through two, three, or four cycles of polymerization; it can be resolved from tubulin by gel filtration chromatography and has an apparent molecular weight of 280,000. Its activity is stimulated 7-fold by cyclic AMP, and resembles the soluble brain protein kinase described by Miyamoto $\text{et al.}$ (1). The microtubule preparation serves as an endogenous substrate for this protein kinase; both 6S and 30S tubulin are substrates for phosphorylation to the extent of about 0.10 ± 0.05 moles/mole.