Defensive steroids from a carrion beetle (Silpha americana)

Summary The defensive anal effluent discharged bySilpha americana in response to disturbance contains a mixture of steroids stemming from a glandular annex of the rectum. The compounds have been characterized as 15-hydroxyprogesterone (1, principal component), 5-pregnan-15-ol-3, 20-dione (2), 5-pregnan-3, 15-diol-20-one (3), 5-pregnan-7, 15-diol-3,20-dione (4), 5-pregnan-3, 7, 15-triol-20-one (5), 5-pregnan-16-ol-3,20-dione (6), and 5-pregnan-3, 16-diol-20-one (7), none previously found in insects. Bioassays with jumping spiders showed compounds1 and6 to be feeding deterrents at the 1 g level.Paper No. 78 of the series: Defense Mechanisms of Arthropods. Study supported by NIH (Grants AI-02908, AI-12020). We thank Maura Malarcher and Maria Eisner for excellent technical help, and the Squibb Institute of Medical Research for samples of authentic reference compounds.     

Neue Synthesen des Chloramphenicols und deren stereochemischen Beziehungen

Summary Two new syntheses of Chloramphenicol are described starting from the diastereoisomers of -phenylserinmethyl ether and cinnamyl alcohol methyl ether respectively. The configurational correlation of the diastereoisomers of -phenylserin-methyl ether with -phenylserin and chloramphenicol is discussed. A new method for transforming erythro--phenylserinol into threo--phenylserinol is described. New examples of the Neighboring group effect were studied. The sterical course of the addition of methylhypobromite to the double bond is discussed.     

Modification of digitalis inotropism by a lactam derivative

Resumen Se describe la sintesis y prueba de estructura del 3-acetato de (20 S, 21 R)-3-hidroxi-21-amino-14, 21-oxidonorcolan-23-oico ácido lactama, el cúal es el derivativo lactama de digitoxigenina. Dicho compuesto posée insignificantes efectos inotrópicos, pero inhibe o retarda la acción inotrópica positiva del 3-acetato de digitoxigenina cuando se ensaya en atria izquierda aislada de cochinillo de Indias o conejo.     

The molecular structure of the benzilic acid rearrangement product of 3α, 17β-diacetoxy-11-hydroxy-12-oxo-5β-androst-9(11)-ene

Zusammenfassung Die Struktur desp-Brombenzoates des Benzilsäureumlagerungsproduktes von 3, 17-Diacetoxy-11-hydroxy-12-oxo-5-9(11)-androsten wurde durch dreidimensionale Röntgenstrukturanalyse eines Einkristalls als 3-p-Brombenzoat des 11-Carboxy-3, 11, 17-trihydroxy-13-C-nor-5-androstan 11a, 17-Laktons erkannt.     

Isolement et identification du 5β-prégnane 11β, 17α, 21-triol 3, 20-dione (Dihydrocortisol) dans l'urine humaine

Summary 5-pregnane 11, 17, 21-triol 3, 20-dione (dihydrocortisol) has been isolated and identified in the urine of patients with feminizing adrenal cortical cancer. This steroid showed the same Rf as synthetic dihydrocortisol in six different chromatographic systems. After acetylation, its Rf was the same as that of 21 monoacetate of dihydrocortisol. After bismuthic or chromic oxydation, it had the same chromatographic Rf as 5-androstane 11-ol 3, 17-dione and 5-androstane 3, 11, 17-trione respectively. After chromic oxydation of its acetate, the Rf was the same as that of 21 monoacetate of cortisone.     

Synthese von 5α- und 5β-Androstan-17β-ol-3-on-17-acetat aus Hyodesoxycholsäure

Summary 5- and 5-androstane-17-ol-3-one-17-acetate have been prepared from 5-androstane-6, 17-diol-3-one-17-acetate by a synthesis involving directedHuang-Minlon-reduction.Separation of 5-androstane-17-ol-3-one from its 5-isomer could readily be achieved by crystallisation of their 3-ethylenketals from acetone.     

Delay in skin allograft rejection in rats grafted with fetal adrenal glands

Resumen Se ha observado en este trabajo que el injerto de suprarrenales de fetos en ratas de 6 días de edad determina aumento del tiempo de supervivencia de aloinjertos de piel realizados al 10° día de vida en relación a los testigos y a ratas injertadas con suprarrenales de adulto. Un efecto similar se observó cuando se administró diariamente a partir del 6° día de vida 16-metil prednisona en dosis altas que producían gran trastorno del crecimiento, evidente disminución de peso del timo y en algunos casos muerte del animal.

---

---

Fellow of the Consejo Nacional de Investigaciones Centificas y Técnicas (Argentina).     

Tetrapyrrole biosynthesis from 4,5-dioxovaleric acid inRhodopseudomonas spheroides

Summary Porphyrin biosynthesis from 4,5-dioxovaleric acid was studied in cell suspensions ofR. spheroides. The experiments show that 4,5-dioxovaleric acid is a far precursor of porphyrins through amino laevulinic acid formation in a transamination reaction involving also 1-alanine. It differs radically from the classical aminolaevulinic acid synthesis using glycine and succinyl CoA as substrates.Acknowledgments: The authors are indebted to Dr Rodolfo García for helpful discussions and criticisms. Special thanks are given to Dr Aldo Mitta and other members of the Comisión Nacional de la Energía Atómica for their continuous help and support and for using their facilities in order to synthetise DVA.     

Caractérisation de laβ-galactosidase d'Helix pomatia par immunoélectrophorèse

Summary Digestive juice ofHelix pomatia was studied by immunoelectrophoresis: after incubation with a chromogenic substrate, 5-bromo-4-chloroindol-3-yl--D-galactopyranoside, two-galactosidases were revealed.     

Ein neues Verfahren zur Herstellung von 19-Norsteroiden

Summary The new methods for the production of 19-norsteroids described involve the conversion of 5-halogen-6-hydroxy-steroids into the corresponding 5-halogen-6:19-ethers either with lead tetraacetate or by the hypoiodite reaction^8,10. The 6:19-oxygen bridge is then opened reductively either directly or after oxidation of the 6:19-ethers to lactones or preferably after introduction of a ^4,6-3-oxo grouping. Acylolytic cleavage of the ⁴-3-oxo-6:19-ethers followed by alkaline hydrolysis gives ^4,6-3-oxo-19-hydroxy-steroids. The 19-hydroxycompounds formed are easily converted into 19-norsteroids by known methods.

---

---

Über Steroide, 189. (vorläufige) Mitteilung; 188. Mitt. vgl.J. Kalvoda, J. Schmidlin, G. Anner undA. Wettstein, Exper.18, 398 (1962).     

Purification and characterization of aβ-glucosidase (linamarase) from the haemolymph ofZygaena trifolii Esper, 1783 (Insecta,Lepidoptera)

Summary A -glucosidase (linamarase) was purified 52-fold with a recovery of 27% from the haemolymph of the larvae ofZygaena trifolii, ESPER, 1783 (Lepidoptera, Zygaenidae). The final enzyme preparation was found to be nearly homogeneous on both disc polyacrylamide gel electrophoresis and SDS-polyacrylamide gel electrophoresis. The molecular weight of the enzyme was determined to be about 130 kDa; it consisted of two subunits of about 66 kDa. The enzyme showed an optimum between pH 4.5 and 5 with linamarin and a broad optimum between pH 3.5 and 6.5 for p-nitrophenyl--D-glucoside; the temperature optimum was 40°C. The -glucosidase showed a high specificity for its endogenous substrates linamarin and lotaustralin. Among the other natural and artificial substrates tested, only prunasin and p-nitrophenyl--D-glucoside were hydrolyzed by the enzyme, whereas linustatin, salicin, cellobiose and trehalose were not. The enzyme is strongly inhibited by -glucosylpiperidine.     

In situ noradrenaline-induced stimulation of dog thyrotrophic secretion

Summary Anterior pituitary microinfusions of noradrenaline in the dog causes a significant release of TSH while adrenaline and dopamine do not.This study was supported by Grant No. S1-049 from the Consejo Nacional de Investigaciones Cientificas y Tecnológicas, Grant No. 281 from the Consejo de Desorrallo Cientifico y Humanístico, Central University of Venezuela, and Fundación José María Vargas.     

The antifertility action of α-chlorohydrin: metabolism by rat and boar sperm

Summary The male antifertility agent -chlorohydrin (I) is metabolized by rat and boar sperm to -chloroactaldehyde (III), -chlorolactate (IV) and Cl^– and not to the proposed active metabolite, -chlorohydrin-1-phosphate (III). It is proposed that -chlorolactaldehyde is produced intracellularly by a specific enzyme and that this is the metabolite responsible for the species-specific antifertility activity of -chlorohydrin.This work was supported by The National Health and Medical Research Council of Australia.     

The distribution of some enzymes involved in the steroidogenesis of hen's ovary

Riassunto È stata studiata con metodi istochimici la distribuzione della ⁵-3-idrossisteroide deidrogenasi ( ⁵-3-HSDH) e delle 17-idrossisteroide deidrogenasi (17-HSDH), DPN- e TPN-dipendenti, nell'ovario di gallina ovulante. Mentre la ⁵-3-HSDH è presente in tutti i tessuti a secrezione steroide dell'ovario, la 17-HSDH è localizzata solo nelle cellule della granulosa.     

Retroaldol transformations in the westphalen diol series

Zusammenfassung Durch Behandlung mit Kalilauge erleidet 5-methyl-19-norcholestan-9, 10-diol-3, 6-dione eine Retroaldolisomerisierung unter Bildung des 10-Hydroxy-Isomers. Letzteres wurde als Hemiketalderivat isoliert. Bei drastischer Behandlung mit Alkali gehen beide Isomere in ein Anthrasteroid über.     

Die Wirkung von Progesteron und Progesteronmetaboliten auf das Wachstum von embryonalem Knorpel in vitro

Summary Embryonic chick bones were cultured in vitro in the presence of progesterone and of a series of progesterone metabolites. It was found that only 5-pregnane-3,20-dione, 3-hydroxy-5-pregnane-20-one, and ⁴-pregnene-20-ol-3-one influence the growth of bones in vitro in a manner similar to progesterone. All other investigated progesterone metabolites exert either a different or no demonstrable action on bone growth.     

Comparison of sterol composition and transformation in chicken and pigeon intestines

Zusammenfassung Es bilden sich 5-Stanol-Derivate von Sterolen im Verdauungstrakt des Huhns, nicht aber bei der Taube. Die intestinalen Gewebe beider Vögel bevorzugen bei ihrer Resorption Campesterol vor -Sitosterol.     

16-β-methylprednisone from hecogenin

Zusammenfassung Es wird über die Herstellung des 16-Methylprednisons berichtet, welche vom Hecogenin ausgehend über ca. 15 Stufen durchgeführt wird. Als wichtige Zwischenstufe treten 5-Pregn-16-en-3-ol-11, 20-dion-Acetat und 16-Methylen-5-pregnan-3, 17-diol-11, 20-dion auf: letzteres wird durch eine stereospezifische katalytische Reduktion in das entsprechende 16-Methyl-derivat umgewandelt.     

Synthese von Solanidin aus Demissidin

Summary The steroidal alkaloid solanidine (solanid-5-ene-3-ol, II) which occurs in the potato plantSolanum tuberosum L. has been synthesized from demissidine (5-solanidane-3-ol, I), an alkaloid from the Mexican wild potatoSolanum demissum Lindl. The synthesis involves the following steps: 5-solanidane-3-one, 2,4-dibromo-5-solanidane-3-one, solanid-4-ene-3-one, 3-acetoxy-solanida-3,5-diene, and solanidine (II).

---

---

Solanum-Alkaloide. XVII. Mitteilung. — XVI. Mitteilung:K. Schreiber undG. Adam, Exper.17, 490 (1961).