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.     

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.     

Acyclic diterpenes containing 3 enol acetate groups from the green algaChlorodesmis fastigiata

Summary 2 new diterpenes, chlorodesmin (4) and dihydrochlorodesmin (5), each containing 3 enol acetate groups, have been isolated from Great Barrier Reef collections of the green algaChlorodesmis fastigiata (Chlorophyta, Caulerpales). Didehydrotrifarin (3) was also characterized.     

Structure assignments of two new C-18-oxygenated steroidal ketals isolated from a pacific soft coral of the genusSinularia

Summary Two new C-18-oxygenated sterols possessing a spiroketal function (1 and2) have been isolated from a soft coral of the genusSinularia. The proposed structures are based on spectral data.     

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.     

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.     

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.     

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.     

Alarm pheromones from the Mediterranean opisthobranchHaminoea navicula

Summary Structure and absolute stereochemistry of two new 3-alkylpyridines, haminol-A (3) and haminol-B (4), isolated from the cephalaspidean molluscHaminoea navicula, have been determined by means of spectral and chemical methods. Haminols are secreted byH. navicula when it is molested, and these induce an alarm response in trail-following conspecifics.In part presented at the 32nd IUPAC Congress Stockholm, 2–7 August 1989. Cimino, G., and Sodano, G., Abstracts SL 302, p. 63.     

Zwei neue Sesquiterpene mit Isosativangerüst ausHelminthosporium sativum

Summary The structure of two new sesquiterpene metabolites ofHelminthosporium sativum, previously assigned to the sativene series, has been settled as in4 and14 by chemical correlation.     

Lucibufagins,IV. New defensive steroids and a pterin from the firefly,Photinus pyralis (coleoptera: Lampyridae)

Summary Two new defensive steroids (lucibufagins6 and7) and a fluorescent pterin (8) have been isolated and characterized from the fireflyPhotinus pyralis.Acknowledgment. We are grateful to the Fonds National Suisse de la Recherche Scientifique (bourse de relève to M.G.). Partial support of this work by the NIH (grants No. AI 12020 and AI 02908), the NSF (grant No. PCM-77-25807), and the American Heart Association is acknowledged with pleasure. Paper No. 66 of the series Defense Mechanism of Arthropods.     

Cardenolide glycosides from the adults and eggs ofChrysolina fuliginosa (Coleoptera: Chrysomelidae)

Besides the known sarmentogenin 3-O--D-allopyranoside (1) and digitoxigenin-3-O-[-D-xylopyranosyl-(14)-2, 3-di-O-acetyl--D-allopyranoside] (4), four new cardiac glycosides (2, 3, 5 and6) have been isolated from the defensive glands of adults ofChrysolina fuliginosa. The structures of the new compounds were determined by¹H NMR at 600 MHz and FABMS. Compounds1–6, present in the adults ofC. fuliginosa, have also been identified in the eggs.     

Milanjilactones A and B,two novel cytotoxic norditerpene dilactones fromPodocarpus milanjianus Rendle

Summary Two new cytotoxic norditerpene dilactones, milanjilactones A(3) and B(4) have been isolated from the stem bark ofPodocarpus milanjianus Rendle and characterized, on the basis of spectroscopic evidence, as 1,2-dehydro derivatives of nagilactones F(1) and G(2).The authors acknowledge the technical assistance of Ms Teresa K. Lightner. Part 11 in the series Potential Antitumor Agents.     

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.     

Taxuspine D,a new taxane diterpene fromTaxus cuspidata with potent inhibitory activity against Ca2+-induced depolymerization of microtubules

A new taxane diterpenoid, taxuspine D (1), possessing an enolacetate moiety, has been isolated from stems of the Japanese yewTaxus cuspidata Sieb. et Zucc., and the structure elucidated on the basis of spectroscopic data. Taxuspine D (1) markedly inhibited Ca²⁺-induced depolymerization of microtubules.     

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.     

Annonacin,a novel,biologically active polyketide fromAnnona densicoma

Summary A new linear polyketide, Annonacin (I), has been isolated from active extracts of the stembark ofAnnona densicoma Mart. Annonacin (I) is highly cytotoxic and is active in an assay designed to detect antimitotic agents. The structure of (I) was determined by analysis of spectroscopic data.25 September 1986     

Antidesmanol-a new pentacyclic triterpenoid fromAntidesma menasu Miq. ex. Tul.

Summary Antidesmanol (1), a new pentacyclic triterpenoid, has been isolated along with n-tritriacontane, friedelin, canophyllal and canophyllol from the aerial parts ofAntidesma menasu. Based on chemical and spectroscopic evidence, its structure has been established as 3-keto-16-hydroxyfriedelane. n-Tritriacontane and friedelin have shown antiinflammatory and diuretic activities respectively in experimental animals.CDRI Communication No. 2536.     

Vidalols A and B,new anti-inflammatory bromophenols from the Caribbean marine red algaVidalia obtusaloba

Chemical studies of the Caribbean red algaVidalia obtusaloba have resulted in the isolation of two new bromophenolic metabolites, vidalols A and B (1, 2). The new compounds were discovered as part of an organized effort to isolate new naturally-occurring anti-inflammatory agents with a focus upon those which may function through the inhibition of phospholipase A₂.