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.     

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.     

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.     

Pectinoacetals A-C: novel sterol hemiacetals from the gorgonianCtenocella pectinata

Three polyhydroxylated sterol hemiacetals, pectinoacetals A-C (1–3) have been isolated as their acetyl derivatives (4–6) from the acetic anhydride treated organic extract of the Indo-Pacific gorgonianCtenocella pectinata. These natural products were found to undergo very rapid epimerization at the C-18 chiral center and thus exist only as an equilibrium mixture of two diastereomers. The structure assignments are based on spectral studies and chemical modifications of the natural products.     

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).     

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.     

New norsesquiterpene aldehyde and sesquiterpene hemiacetal from the seed ofPolygonum hydropiper

Summary A new norsesquiterpene aldehyde, polygonal and a new sesquiterpene hemiacetal, isodrimeninol having drimane skeleton have been isolated from the seed ofPolygonum hydropiper, and their structures have been established to be1 and5. Polygonal showed pungency and plant growth inhibitory activity.     

Two derivatives of farnesylacetone from the brown algaCystophora moniliformis

Summary Farnesylacetone epoxide (3) and the isomeric diketone (4) have been isolated from the brown algaCystophora moniliformis.Acknowledgment. We thank Dr K. Noack for CD measurements and interpretations and Mr K. Harada for algal identification.     

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.     

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.     

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.     

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.     

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.     

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.     

Zonaroic acid from the brown seaweedDictyopteris undulata (=zonarioides)

Summary A sesquiterpene-substituted 4-hydroxybenzoic acid, zonaroic acid (5), is described from the brown seaweedDictyopteris undulata (=zonarioides). The absolute stereochemistry in the zonarol (1)-chromazonarol (2) and zonaroic acid (5) series has also been defined. The occurrence of5 along with zonarol (1), the corresponding sesquiterpene-substituted hydroquinone, suggests that 4-hydroxybenzoic acid is the ring precursor as in ubiquinone biogenesis.     

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.     

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.     

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.     

Transformation of progesterone byCaldariella acidophila,an extreme thermophilic bacterium

Summary Caldariella Acidophila, a thermophilic bacterium, converts porgesterone (1) to pregn-4-en-3,6,20-trione (2), 5a-pregnan-3, 6, 20-trione (3), pregn-4-en-20a-ol-3-one (4), pregn-4-6-ol-3, 20-dione (5) and pregn-4-en-6a-ol-3, 20-dione (6). Different patterns of these metabolites were obtained by modifying the incubation conditions and using differently treated biocatalysis.