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.     

Luffariellolide,an anti-inflammatory sesterterpene from the marine spongeLuffariella sp.

Summary Luffariellolide (2) is a sesterterpene from the Palauan spongeLuffariella sp. that has useful anti-inflammatory properties. In contrast with the irreversible action of manoalide (1) on phospholipase A₂, luffariellolide (2) is a slightly less potent but partially reversible PLA₂ inhibitor.30 December 1986Acknowledgment We thank Edward Luedtke, Elise Clason and Ellen Snideman for performing some of the assays reported above. The sponge was identified by Dr. Klaus Rützler, Smithsonian Institution, Washington, D.C. The research was supported by grants from Allergan Pharmaceuticals and the California Sea Grant College Program (Projects R/MP-30 and R/MP-31).     

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.     

Furodendin,a C22 degraded terpene from the spongePhyllospongia dendyi

Summary The structure of furodendin (5), a minor secondary metabolite of the spongePhyllospongia dendyi, has been solved by spectral methods. Furodendin is probably derived, biosynthetically, by elimination of a C₃ unit from a C₂₅ geranyl-farnesol precursor.Acknowledgment. We thank Dr C. Evans for sponge identification, RRIMP Museum number FN 1516/000.     

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.     

Über die Wirkung von rac-endo-2-Bornanamin und von verwandten Verbindungen gegen Influenza A2-Virus Asia

Summary rac-endo-2-Bornanamine (1) shows good activity against infections with influenza A₂ virus (Asia) in mice. None of 41 derivatives or analogues was superior to compound1.     

6,10,14-Trimethylpentadecan-2-one and 6,10,14-trimethyl-5-trans, 9-trans, 13-pentadecatrien-2-one from the androgenic glands of the male crab Carcinus maenas

Summary 2 C₁₈ isoprenoid ketones, hexahydrofarnesylacetone (1) and farnesylacetone (2) have been identified for the first time in lipid extracts from the androgenic glands of the male crab Carcinus maenas, using coupled gas chromatography-mass spectrometry. The 2 compounds prepared by synthesis, are biologically active, inhibiting the incorporation of³H-leucine in Crustaceans ovaries subcultures.We wish to thank Professors H. Charniaux-Cotton and E. Lederer for their permanent interest in this work.     

Structure of victorin C,the major host-selective toxin fromCochliobolus victoriae

Summary The predominant host-selective toxin fromCochliobolus victoriae, victorin C, is a peptide with an apparent mol. wt of 796, representing a cyclic array of the subunits1–6. The structure of the toxin has now been established as in16 through analysis of the degradation products generated by enzymic and non-enzymic partial hydrolysis. The presence of a hydrated aldehydo group requires for victorin C the composition C₃₁H₄₅O₁₃N₆Cl₃ with an amended mol. wt of 814, for which independent experimental support has been secured.     

Furospongolide,a new C21 furanoterpene from a marine organism

Summary The structure of a new linear C₂₁ furanoterpene, furospongolide (1), obtained from the marine spongeDysidea herbacea, was determined by spectral means.We thank Professor J. Vacelet for the identification and Dr Loya and Mr Benayahu for the collection of the sponge.     

Isometachromin,a new cytotoxic sesquiterpenoid from a deep water sponge of the family Spongiidae

Isometachromin (1), a new sesquiterpene-quinone that is related structurally to metachromin C (2), and the known compounds ilimaquinone (3) and and 5-epi-ilimaquinone (4), were isolated from a deep water sponge in the family Spongiidae; the structure of isometachromin was elucidated by spectral methods. Isometachromin exhibits in vitro cytotoxicity against the human lung cancer cell line A 549 (IC₅₀=2.6 g/ml), but not against P 388 murine leukemia (IC₅₀10 g/ml) and also exhibits antimicrobial activity.This research is Harbor Branch Oceanographic Institution (HBOI) contribution number 911. We thank Drs S. A. Pomponi and M. Kelly-Borges (HBOI) for sponge taxonomy, and Dr P. McCarthy and T. Peterson (HBOI) for antimicrobial data.     

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.     

Cocarcinogens of the diterpene ester type fromCroton flavens L. and esophageal cancer in Curaçao

Summary From the roots ofCroton flavens L., 3 highly irritant and tumor promoting Croton factorsF ₁–F ₃ and the corresponding 3 cryptic Croton factorsF₁–F₃ were isolated and characterized as novel esters of 16-hydroxy- and 4-deoxy-16-hydroxyphorbol, respectively. These findings suggest that tumor promoters of the phorbol ester type, ingested through the widespread and frequent use ofCroton flavens according to local habits, may be causally related to the well recognized high rate of esophageal cancer on Curaçao.Dedicated to Prof. Dr H. P. Rusch, Director Wisconsin Clinical Cancer Center, Madison, Wis. USA, on occasion of his 70th birthday. We wish to thank Dr J.F. Morton, Morton Collectanea, University of Miami, Florida, USA, for kindly supplying us with the plant material.     

Enantiomeric cannabinoids: stereospecificity of psychotropic activity

Summary The 1,1-dimethylheptyl homolog of (–)-(3R,4R)-7-hydroxy-delta-6-tetrahydrocannabinol (compoundII) is highly psychotropic in mice, rats and pigeons. The (+)-(3S,4S) enantiomer (III) was found to be psychotropically inactive at doses up to several thousand times those of the ED₅₀ of (II).We thank Dr A. Breuer and Mrs H. Amsalem for help with the syntheses. The research reported above was supported in Tucson by NIH grant NS 15441; in Uppsala by grants from the Swedish Medical Research Council (5757) and the Swedish Council for the Planning and Coordination of Research (84/2082); in Jerusalem by the Szold Foundation.Presented in part at a meeting at the US National Institute on Drug Abuse, Washington, D.C., October 1986, see NIDA Research Monographs79 (1987) 15.     

Luffolide,a novel anti-inflammatory terpene from the spongeLuffariella sp.

Summary Luffolide (4) is a minor metabolite of the spongeLuffariella sp. from Palau. The structure of luffolide was determined by single crystal X-ray analysis. Luffolide is relatively unstable and undergoes a complex cyclization reaction to give the hexacyclic products5 and6. Luffolide (4) has some of the anti-inflammatory properties of manoalide (1): this may help to define the chemical reaction between manoalide (1) and phospholipase A₂.All crystallographic calculations were done on a PRIME 9950 computer operated by the Cornell Chemistry Computing Facility. Principal programs employed were: FOBS, a data reduction program by G.D. Van Duyne, Cornell University, 1987; MULTAN 80, and RANTAN 80, systems of computer programs for the automatic solution of crystal structures from X-ray diffraction data (locally modified to perform all Fourier calculations including Patterson syntheses) written by P. Main, S. E. Hull, L. Lessinger, G. Germain, J. P. Declercq and M. M. Woolfson, University of York, England, 1980 BDLS, an, anisotropic block diagonal least squares refinement written by K. Hirotsu, E. Arnold, and G. D. Van Duyne, Cornell University, 1987; PLUTO 78, a locally modified crystallographic illustration program by W. D. S. Motherwell, Cambridge Crystallographic Data Centre, 1978; and BOND, a program to calculate molecular parameters and prepare tables written by K. Hirotsu and G. Van Duyne, Cornell University, 1985.Acknowledgment. We thank the Government of the Republic of Palau for a scientific research permit. We thank Dr Klaus Rützler, Smithsonian Institution, Washington, D.C. for identifying the sponge and Mary Kay Harper for performing additional bioassays. This research was supported by grants from the Sea Grant College Programs of California [Projects R/MP-30 to DJF) and R/MP-31 (to RSJ)] and New York (to JC) and the National Institutes of Health (CA 24487 to JC).     

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.     

Metal complex formation by nicotianamine,a possible phytosiderophore

Summary The acid dissociation constants of nicotianamine (1) (pK₁=6.97, pK₂=9.13, pK₃=9.75; 0.1 M KClO₄, 25°C) and the stability constants for its 11 complexes with bivalent metal ions (log K_Cu=18.6, log K_Ni=16.1, log K_Co=14.8, log K_Zn=14.7, log K_Fe=12.1, log K_Mn=8.8, log K_Mg4.5; 0.1 M KClO₄, 25°C) were determined using potentiometric titrations in aqueous solution. Fe(III)-nicotianamine complexes were not detected under the same experimental conditions.Part 13 in the series On the normalizing factor for the tomato mutantchloronerva, for part 12 see Ripperger et al.⁴.     

The rate of action of cyclic ammonium and sulfonium analogues of acetylcholine

Summary The rate of action of cyclic acetylcholine analogues in the 4-acetoxypiperidine and 4-acetoxythiacyclohexane series has been determined by using the isolated left guinea-pig atrium. The kinetic data obtained has been correlated with the experimental ED₅₀-value on the muscarinic receptor.Structure and Conformation Activity Relationships of Cyclic Acetylcholine Analogues.VI.We thank the German Research Association for supporting this work, and Mrs Ch. Röttger for her valuable assistance in carrying out the investigations.     

Thiamine-quinone adducts. Colorimetric determination of thiamine

Summary 2, 3-dichloro-1,4-naphtoquinone reacts with thiamine in the presence of NH₃ to give a 12 adduct, for which structureII is proposed on the basis of analytical and spectroscopic (IR) data. Such a reaction is very useful for thiamine quantitative determination.     

Identification of a plant growth inhibiting iridoid lactone fromDuroia hirsuta,the allelopathic tree of the ‘Devil's Garden’

Bioactivity-directed fractionation of a root extract ofDuroia hirsuta (Rubiaceae), a toxic and potentially allelopathic understory tree from the western Amazon, has led to the isolation of the tetracyclic iridoid lactone, plumericin (1). Bioassays showing plumericin strongly inhibited lettuce radicle elongation at a concentration (IC₅₀) of 35.8 m/ml (123 M). The isolation of a highly potent inhibitor of plant growth fromDuroia hirsuta supports the hypothesis that the lack of vegetation surrounding this tree is the result of allelopathy.