Minor sesquiterpenoids from the sponge Axinella cannabina

Summary On the basis of chemical and spectral evidence, the structureIV has been assigned to Axisonitrile-4, an axane-sesquiterpenoid isonitrile, isolated from the spongeAxinella cannabina; in the same organism have been also found Axisothiocyanate-4 (V) and Axammide-4 (VI).This investigation was supported by a grant of the Consiglio Nazionale delle Ricerche, Rome (NA 75.00770.03).     

Further sesterterpenes from the spongeSpongia nitens: 12-epi-scalaradial and 12,18-diepi-scalaradial

Summary 2 new tetracarbocyclic sesterterpenes, isomers of the previously² described scalaradial (1), have been isolated from the marine spongeSpongia nitens and their structures have been established to be2 and3; during the structural work, evidence on the stereochemistry of1,2 and3 has been obtained.This work is part of the Progetto Finalizzato per l'Oceanografia e i Fondi Marini, C.N.R., Roma. We thank the Zoological Station (Naples) for the collection of the sponge, A. Crispino, C. Di Pinto and A. Milone for their technical assistance and Prof. C. Santacroce for generous gifts of scalaradial.     

Leonurine,an improved synthesis

Summary Leonurine (1) is the uterotonic principle ofLeonurus artemisia. We have developed a simple, high-yield synthetic procedure of1 that is adaptable to large scale preparation. The synthesis involves the condensation of syringic acid and 4-guanidino-1-butanol hydrochloride in the presence of DDC using 11 HMPT-ether as solvent. The synthetic leonurine showed uterotonic activity in vivo and in vitro.Acknowledgment. This work was partly supported by World Health Organization, Geneva, Switzerland.     

A non-peroxide norsesterterpene from a marine spongeHyrtios erecta

Summary A new norsesterterpene, hyrtial4, and known sesterterpenes,1–3, have been isolated from an anti-inflammatory active crude extract of the spongeHyrtios erecta.This sponge,Hyrtios (Heteronema) erecta Keller 1889, collected in 1980/81, from Tonga was extremely abundant in the Vava'u Is. Group.We thank Prof. R. Jacobs and his research group at UCSB for this data.     

Guggulsterol-like steroids from the Mediterranean gorgonianLeptogorgia sarmentosa

Summary Several polyoxygenated steroids (1, 2, 3) have been isolated from the marine gorgonianLeptogorgia sarmentosa. One of these (1) is the known guggulsterol III, previously found in the pharmacologically active resin from the treeCommiphora mukul; the others,2 and3, have not been found before in nature, and are closely related to1. During the structural work apparent anomalies in the CMR-spectra of1 were observed.The authors are grateful to Prof. Sukh Dev for the PMR-spectra of guggulsterol III. Thanks are also due to Zoological Station (Naples), for the collection of the gorgonian, to Centro Metodologie Chimico-Fisiche, Università di Napoli, for recording PMR-spectra on WH-270 Superconducting Spectrometer-Bruker, to Mr C. Di Pinto for the CMR-spectra and to Mr A. Milone for the MS spectral measurements.     

The antifertility action ofa-chlorohydrin: Enzyme inhibition bya-chlorohydrin phosphate

Summary Preparations of the enzymes glyceraldehyde-3-phosphate dehydrogenase and triosephosphate isomerase are shown to be inhibited bya-chlorohydrin phosphate (II) in a competitive and non-competitive manner, respectively.a-Chlorohydrin (I), glycidol and epi-chlorohydrin have no inhibitory activities suggesting that their antifertility actions are due to their metabolism in vivo toa-chlorohydrin phosphate.     

Characterization of victorin C,the major host-selective toxin fromCochliobolus victoriae: Structure of degradation products

Summary Several host-selective toxins have been isolated in pure form culture filtrates ofCochliobolus victoriae. Acid hydrolysis of the major toxin, victorin C (apparent mol.wt 796), produced five fragments to which structures1–5 have been assigned. Spectroscopic techniques revealed that the toxin contains an additional subunit corresponding to6; thus all the components of victroin C are accounted for.     

Correlation of anthothecol and hirtin

Summary Hirtin (3) and anthothecol (2) have been correlated by conversion of each to the derivative (10).     

Further perhydroazulene diterpenes from marine organisms

Summary 3 novel diterpenes,4–6, having the perhydroazulene skeleton already found in pachydictiol A (1) and dictyol A (2) and B (3), have been isolated from both the digestive gland of Aplysia depilans and algae of the family Dictyotaceae.     

Specific inhibition of human leukocyte elastase by substituted alpha-pyrones

Summary Severala-pyrones have been synthesized and investigated for their in vitro inhibitory activity usinga-chymotrypsin (a-CT), porcine pancreatic elastase, (PPE) and human leukocyte elastase (HLE). 4-Hydroxy-6-undecyl-2H-pyran-2-one4, 4-Hydroxy-6-[(1-butyl)heptyl]-2H-pyran-2-one5 and 4-Methoxy-6-[(1-butyl)heptyl]-2H-pyran-2-one6 were found to be specific inhibitors of HLE. These compounds constitute a promising new class of HLE inhibitors.Acknowledgments. We are grateful to the Petroleum Research Fund of the American Chemical Society (Grant No. 13058-B4), the American Lung Association and the Office of Sponsored Research of Wichita State University for generous financial support of this work. This work was also supported by NHLBIGrant 5PO1HL20994 and the Council for Tobacco Research, USA-Inc. Grant 901B.     

Chemical defense in the three European species ofCrematogaster ants

The composition of the Dufour gland of the antC. scutellaris has been reinvestigated by gas chromatography/mass spectrometry. The major components of the gland are (2E,5E,12Z)-4-oxoheneicosa-2,5,12-trien-1-ol acetate (1a) its ¹⁴ and ¹⁶ double bond isomers (1b and1c), and the corresponding (Z,Z)-dienes5a and5b, all containing an acetylated C₂₁ chain. The previously proposed structures1d, 1e, and5c, which are based on an homologous acetylated C₂₃ chain, correspond to minor derivatives present in the gland. Traces of acetylated C₁₉ homologs, tentatively identified as1g-1i, have also been found. The Dufour gland contents of the two other EuropeanCrematogaster species have also been studied.C. auberti is very similar toC. scutellaris in producing mainly1a, 1b and1c, together with the same higher and lower homologs, but it lacks the dienic derivatives5, whereasC. sordidula contains essentially the acetylated C₁₉ compounds1g, 1h, and1i, accompanied by acetylated C₁₇ homologs.     

New bibenzyls of the liverwort,Radula variabilis

Summary 3 new bibenzyls having a 7-membered heterocyclic ring have been isolated from the liverwort,Radula variabilis and their structures have been established to be1, 3 and5.     

Ein bicyclischer Abkömmling von (−)-longifolen ausHelminthosporium sativum undH. victoriae

Summary (–)-Longifolene,4, and a new secolongifolane derivative, shown to possess structure5, have been isolated fromHelminthosporium sativum andH. victoriae.     

Cortinarins inCortinarius speciosissimus? A critical revision

Summary Fluorescent cyclic decapeptides, the so-called cortinarins, have been claimed to cause the toxicity of the deadly poisonous mushroomCortinarius speciosissimus. As the structure elucidation described in the literature is doubtful in decisive parts, the proposed structures must be disputed. The present study demonstrates that the fluorescence is mainly due to ergosta-4,6,8 (14),22-tetraen-3-one (8) and to photodecomposition products of the nephrotoxin orellanine (1). Moreover, we were not able to reproduce the isolation of fluorescent or any other cyclic peptides related to cortinarins fromC. speciosissimus, by various methods.     

Marine antitumor agents: 14-deoxycrassin and pseudoplexaurol,new cembranoid diterpenes from the Caribbean gorgonianPseudoplexaura porosa

Two new cytotoxic antitumor diterpenoids of the cembrane class, named 14-deoxycrassin (3) and pseudoplexaurol (4), have been isolated from the Caribbean gorgonian octocoralPseudoplexaura porosa. The structure of lactone3, possessing the infrequently encountered -methylene--lactone ring, has been established from spectral and chemical data and that of alcohol4 has been established from spectral data.     

Furan fatty acid steryl esters from the marine spongeDictyonella incisa which show inflammatory activity

Summary Three new furan fatty acids, (9Z, 19Z)-3, 6-epoxyhexacosa-3,5,19-tetraenoic acid (1a), (8Z, 11Z, 14Z, 17Z)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (2a), and (8Z, 11Z, 14Z, 17E)-3, 6-epoxyeicosa-3,5,8,11,14,17-hexaenoic acid (3a), and a new polyunsaturated fatty acid (5Z, 8Z, 11Z, 14Z, 17E)-eicosa-5,8,11,14,17-pentaenoic acid (6a), present in the spongeDictyonella incisa as the respective steryl esters, have been isolated as methyl esters and their structures have been determined by spectral and chemical analysis. The furan fatty acid esters have shown a high inflammatory activity, which suggests their potential role as feeding deterrents.     

ZNS-aktive Phenylpropylamine vonCatha edulis FORSK. (Celastraceae) kenyanischer Herkunft

Summary The phenylpropylamine fraction ofCatha edulis FORSK. grown in Kenya has been investigated. The major components have been found to be (S)-(–)--aminopropiophenone (1), (+)-norpseudoephedrine (2) and(–)-norephedrine (3). Quantitative ratios of1, 2, 3 in tissues of different age are discussed.

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ZNS-aktive Phenylpropylamine vonCatha edulis FORSK. (Celastraceae) kenyanischer Herkunft

     

Constituents of propolis

Summary The major constituents of propolis collected in Western Australia have been isolated and identified as pterostilbene (5), xanthorrhoeol (6), sakuranetin (2) and pinostrobin (1).Acknowledgments. We gratefully acknowledge Dr H. Duewell of the University of Newcastle, New South Wales, for an authentic sample of xanthorrhoeol.     

New aromatic esters of the liverwort,Trichocolea tomentella

Summary 4 new aromatic esters containing isoprene units have been isolated from the liverwort,Trichocolea tomentella, and their structures have been established to be1, 2, 3 and4.The authors are indebted to Professor G. Ourisson of Université Louis Pasteur de Strasbourg, France, and Dr S. Hattori of the Hattori Botanical Laboratory for their helpful suggestion to this work.