Naphthoquinone derivatives from the fungusHendersonula toruloidea

Summary 2 yellow naphthoquinone derivatives were isolated from several pathogenic strains ofHendersonula toruloidea Nattrass. They were identified as 2,7-dimethoxy-6-ethyl-5-hydroxy-1,4-naphthoquinone and 2,7-dimethoxy-5-hydroxy-6-(1-acetoxyethyl)-1,4-naphthoquinone by means of physico-chemical methods.Thanks are due to Mr A.J.M. van Beijnen, Laboratory for Organic Chemistry, State University of Utrecht, for optical rotation measurements.The authors are indebted to Mr C. Versluys, Analytical Laboratory, State University of Utrecht, for measuring the mass spectra.We thank Mr J. W. Marsman, Institute for Organic Chemistry TNO, Utrecht, for the PMR-spectra.     

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.     

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.

---

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

     

Two new kaempferol 3,7-diglycosides and kaempferitrin in the fernAsplenium trichomanes

Summary The fronds of the fernAsplenium trichomanes contain kaempferol 3,7-dirhamnoside (1) and the new compounds kaempferol 3-O-a-rhamnoside-7-O-a-arabinoside (2) and kaempferol 3-O-a-arabinoside-7-O-a-rhamnoside (3). The presence of the above flavonoids has been shown by spectroscopic methods and chemical degradations.Acknowledgments. The author thanks Prof. H. Wagner (Institut für pharmazeutische Arzneimittellehre der Universität München, München) for a sample of kaempferol 3,7-dirhamnoside, Dr K. R. Markham (Chemistry Division, D.S.I.R., Petone, New Zealand) for a gift of pectinase and Mr A. D'Urso (Botanic Institute, University of Catania) for help in acquiring the plant material.     

The structure of amoorastatone and the cytotoxic limonoid 12-hydroxyamoorastatin

Summary 2 new limonoid-type terpenes have been isolated from an aqueous extract of seeds produced by the Eastern Himalayan (India) plantAphanamixis grandifolia Bl. By interpreting principally mass spectral and nuclear magnetic resonance data, the structures of 12-hydroxyamoorastatin (2b) and amoorastatone (3) were elucidated. Unequivocal evidence for the 12-hydroxyamoorastatin structural assignment was obtained by chemical conversion to sendanin (4). Amoorastatin derivative2b was found to significantly inhibit growth of the murine P388 lymphocytic leukemia cell lines but amoorastatone in the same system was inactive. In a comparative biological study, sendanin (4) and anthothecol (7) were also found significantly to inhibit growth of the P388 cell line, while rohitukin (8) and limonin (9) were found to be inactive.Part 63 of the series Antineoplastic Agents. For the previous contribution refer to G.R. Pettit, T.S. Krupa and R.M. Reynolds, Int. J. Peptide Protein Res., in preparation. The present investigation was supported in part by Public Health Research Grant No. CA-16049-05 from the National Cancer Institute, the Fannie E. Rippel Foundation, Mrs Mary Dell Pritzlaff, the Spencer T. and Ann W. Olin Foundation, Mr John F. Schmidt, and the Phoenix Coca-Cola Bottling Company.     

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.     

Structure of two biologically active sesquiterpenoid amino-quinones from the marine spongeDysidea avara

Summary The structures of 2 minor constituents of the marine spongeDysidea avara, which induce developmental aberrations in sea-urchin eggs, are described. The structures were confirmed also by a simple synthesis from avarol (1).Acknowledgments. The authors wish to thank Mr A. Crispino for his skillfull laboratory technical assistance. Thanks are also due to Mr C. Di Pinto (NMR) and Mr A. Milone (MS).     

Five plants of the family Cucurbitaceae with flavonoid patterns of pollens different from those of corresponding stigmas

Summary Flavonoid patterns of pollens of 5 plants of the family Cucurbitaceae are different from those of the corresponding stigmas. The major flavonoid of pollens has been identified as kaempferol 3-O-rutinoside (1). Rutin (2) has been found in stigmas of 2 species. The other flavonoids of pollens and stigmas of these plants are flavonol 3-O-glycosides.Acknowledgment. The author thanks Mr A. D'Urso (Botanic Institute, University of Catania) for help in acquiring the plant material.     

Zur Stereochemie der Propandioldehydrase-Reaktion

Summary Propanedioldehydrase is shown to convert both (+)-(S)-2-²H-propanediol,3, and (–)-(R)-1-²H₂-propanediol,5, to specimens of deuterated propion-aldehyde, for which the (S)-configuration has been established. Thus, in the propanedioldehydrase reaction migration of hydrogen atoms from C–1 to C–2 always occurs with inversion of configuration.     

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.     

The isolation and structure of 13,18-dehydroglaucarubinone,a new antineoplastic quassinoid fromSimarouba amara

Summary An investigation of the Guyana plantSimarouba amara Aubl. (Simaroubaceae) for antineoplastic quassinoids led to isolation and structural determination of the new quassinoids 2-acetylglaucarubine (1a) and 13,18-dehydroglaucarubinone (2). The previously known 2-acetylglaucarubinone (3a) and glaucarubinone (3b) were also obtained. The new quassinoid2 was found significantly to inhibit growth of the murine lymphocytic leukemia P388.Antineoplastic agents 59. For part 58 refer to M. T. Edgar, G.R. Pettit and T.H. Smith, J. org. Chem., in preparation.Acknowledgments. We wish to thank Mr B. Septe for providing the¹³C-NMR-data. Dr Jean H. Schmidt and Miss Linda M. Lange for assistance with biological studies.—G.R. Pettit is grateful to the National Cancer Institute (performed pursuant to contract No. N01-67048 with the Division of Cancer Treatment, NCI, National Institutes of Health, Dept. of Health, Education and Welfare), Public Health Services Research grant No. CA 16049-03 from the National Cancer Institute, the Fannie E. Rippel Foundation, Talley Industries, and the Phoenix Coca-Cola Bottling Co., for partial support of this investigation.     

5-(Hydroxyimino)-4-methoxy-2-(pivaloylimino)thiazolidine-3-acetamide,a reduced nitroheterocyclic derivative with potent schistosomicidal properties

Summary The synthesis and antischistosome properties of 5-(hydroxyimino)-4-methoxy-2-(pivaloylimino)thiazolidine-3-acetamide (1) are described. The compound was prepared by reduction of the nitrothiazoline (2) with stannous chloride in methanol, and represents the first example of a reduced nitroheterocyclic compound showing potent schistosomicidal properties. The possible relationship of compounds such as1 to the as yet unidentified reduced active but toxic entities formed in vivo from nitroheterocyclics like metronidazole is discussed.Acknowledgments. The authors are grateful to Dr A. J. Everett and his staff for the physical chemistry measurements, and to Mr G. Dickerson for the antischistosome testing.     

Chemistry of mediterranean gorgonians. II. Pregna 4,20-dien-11α-ol-3-one acetate,a novel steroid from the gorgonianEunicella cavolini

Summary The compound titled1 has been isolated from the gorgonianE. cavolini and synthesized from 11-acetoxy-progesterone (3).This work has been carried out in the frame of the Progetto Finalizzato per l'Oceanografia e i Fondi marini, C.N.R., Roma. Acknowledgments. We are grateful to the Zoological Station (Naples) for the collection of Gorgonians. Thanks are also due to Mr G. Scognamiglio, for technical assistance and to Mr C. Di Pinto, for NMR-experiments.     

Research Articles¶Naturally occurring 2′-O-methylpurine nucleosides with hypotensive properties

2′-O-Methylinosine (1) has been isolated for the first time and shown to be an intrinsic hypotensive principle. Its probable in vivo precursor, 2′-O-methyladenosine (3), showed stronger and even orally potent hypotensive activity. Resistance of the methyladenosine (3) against adenosine deaminase is thought to contribute to its long-lasting activity. The effect of both nucleosides (1 and 3) was not accompanied with any significant change in heart rate, which is often observed with adenosine. Received 2 October 1997; accepted 28 October 1997     

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.     

On the synthesis of serine and homoserine samples asymmetrically labelled with tritium and deuterium in the hydroxymethylene group

Summary (1 R) [1-³H,²H₁] 3-Phenylpropanol, the key intermediate in the synthesis of (4 R) [4-³H,²H₁] D, L-homoserine and of the (4 S)-isomer, is obtained from (1 S) [1-²H₁] 3-phenylpropanol and (1 RS) [1-³H] ethanol upon incubation with yeast alcohol dehydrogenase and NAD⁺; under similar conditions 2-phenylethanol undergoes very small exchange with [1-²H₂] ethanol.     

Desacetylscalaradial,a cytotoxic metabolite from the spongeCacospongia scalaris

Summary From the marine spongeCacospongia scalaris, scalaradial1, desacetylscalaradial2, and heteronemin3 were isolated. Compound2 showed potent cell growth inhibition. The stereochemistry of3 is briefly discussed.Acknowledgments. The authors are grateful to Prof. T. Hase and Mr R. Nakai for collecting the sponge and to Dr s. Tanida for the sponge identification.     

A simple synthesis of (E)-3-formylbut-2-enenitrile,and its use as a precursor of isotope-labelled zeatin and (±) dihydrozeatin

Summary (E)-3-Formylbut-2-enenitrile (4) is synthesized in 2 steps by reacting pyruvaldehyde dimethylacetal and acetonitrile in the presence of sodium methoxide, followed by acid hydrolysis to give 58% overall yield on distillation. The aldehyde4 can be stepwise and selectively reduced to (E)-3-hydroxymethylbut-2-enylamine (7a) in 37% total yield or exhaustivelyb reduced in 1 step to (±)-4-hydroxy-3-methylbutylamine (6) in 46% total yield. Compound7a and6 can be condensed with 6-chloropurine to give zeatin and (±)dihydrozeatin respectively. This provides a readily accessible method for isotope-labelled zeatin and its derivatives at side chain.Contribution No. 1064, Alberta Research CouncilProcess for the Preparation oftrans-3-formylbut-2-enenitrile S. Chen and J. MacTaggart, patent applicatioin registered in Canada and the United States of America.Acknowledgment. The author thanks Mr J. M. MacTaggart and Mrs C. M. Goulet for valuable experimental assistance and Dr R. M. Elofson for helpful discussions.     

New tigliane and daphnane derivatives fromPimelea prostrata andPimelea simplex

Summary From the methanol extract ofPimelea prostrata, prostratin (I) and 2 autoxidation products have been isolated. They are tigliane derivatives and relatively nonirritant on the mouse ear. The irritant pimelea factor P₅ (IIa) also with a tigliane skeleton and related to mancinellin (IIb), as wellas the irritant diterpene ester pimelea factor P₁ (IIa, simplexin) with daphnane skeleton, were found to be present in bothP. prostrata andP. simplex. Further the irritant homologue of simplexin, pimela factorIIIb was detected inP. prostrata. Some biogenetic consequences of these findings are discussed.Acknowledgment: The authors are deeply indebted to Dr T. Cashmore (Palmerton North, New Zealand) and Dr H. B. Roberts (Sydney, Australia) for kindly supplying plant materials.     

Ecdysteroid conjugates in the ovaries of the silkworm,Bombyx mori: 3-phosphates of 2,22-dideoxy-20-hydroxyecdysone and of bombycosterol

Summary Two novel ecdysteroid conjugates, 2,22-dideoxy-20-hydroxyecdysone 3-phosphate (1) and bombycosterol 3-phosphate (2), as well as four known ecdysteroid 22-phosphate esters, have been isolated and characterized from the ovaries of the silkworm,Bombyx mori.