On the incorporation of geraniol and farnesol into cantharidin (author's transl)

On the incorporation of geraniol and farnesol into cantharidin Earlier investigations [1] have shown that cantharidin (1) is biosynthesized by the male Lytta vesicatoria L. (Meloidae, Coleoptera) from the common terpenoid precursors mevalonate and farnesol (3) . To prove if geraniol (2) is incorporated via farnesol (3) into cantharidin (1) the following geraniols have been synthesized and injected into either larvae or male adult Lytta vesicatoria, partly in a mixture with synthetic 11′, 12-[³H]-farnesol as an internal standard: 2-[¹⁴C]-, 7-[¹⁴C]-, 7′, 8-[¹⁴C]-, 7′, 8-[³H]-geraniol. Unexpectedly, geraniol (2) was not specifically incorporated into cantharidin (1) perhaps due to its higher toxicity or its faster degradation relative to the other precursors before incorporation. The incorporation of U-[¹⁴C]-leucine, U-[¹⁴C]-isoleucine and 1-[¹⁴C]-glucose into cantharidin (1) via their metabolites is evident by degradation studies, whereas 1-[¹⁴C]- and 2-[¹⁴C]-glycine do not serve as precursors for cantharidin (1) .     

Biosynthesis of brevicolline

Conclusions 1. When DL-[2^–14C] tryptophan, sodium [2^–14C] pyrotartrate, sodium [¹⁴/C]-formate, and universally labeled L-[¹⁴C] glutamic acid were introduced through the root system intoCarex brevicollis DC, active brevicolline was obtained.2. Tryptophan and sodium pyrotartrate are precursors of the -carboline moiety of the brevicolline molecule, and sodium formate is a precursor of the N-methyl grouping.3. The introduction of universally labeled L-glutamic acid does not lead to an unambiguous indication of the role of this precursor in the biosynthesis of brevicolline.Khimiya Prirodnykh Soedinenii, Vol. 5, No. 1, pp. 39–43, 1969     

The biosynthesis of the alkaloids of Goebelia pachycarpa

Summary 1. Qualitative and quantitative compositions of the main alkaloids in five development phases of theGoebelia pachycarpa C. A. Mey. have been determined.2. The radioactivities of the alkaloids isolated after feeding the plant with assumed precursors -[2-¹⁴C] lysine and [1,5-¹⁴C] cadaverine — show that vigorous synthesis of alkaloids takes place in the flowering and budding periods.3. The results of an investigation of the oxidation products and of the alkaloids introduced and isolated after the feeding of plants with labelled matrine and labelled sophocarpine show that the alkaloids undergo interconversion without intramolecular changes.V. I. Lenin Tashkent State University. Translated from Khimiya Prirodnykh, Soedinenii, No. 4, pp. 549–552, July–August, 1977.     

Biotinylation of amines with the pentafluorophenyl ester of D-biotin

The synthesis has been effected of the pentafluorophenyl ester of D-biotin by the reaction of D-biotin with bispentafluorophenyl carbonate or pentafluorophenyl trifluoroacetate. The possibility has been shown of using the ester obtained for the biotinylization of amino acids and NH₂-containing macromolecules, and D-biotinyl--aminocaproic acid and -[¹⁴C]glycine have been synthesized. It is proposed to use the biotinyl-[¹⁴C]glycine for measuring the activity of avidin.Institute of Molecular Biology, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 404–408, May–June, 1989.     

Preparation of some carbon-14-labeled amino acids by radiophotosynthesis using sugar beet plant

Radiophotosynthesis has been applied as a means for preparing a number of carbon-14-labeled amino acids using sugar beet plants grown under controlled environmental conditions. The apparatus used, conditions of operation, isolation of products, and their analysis and radiometry have been discussed in detail. From the results obtained, it can be inferred that a number of labeled amino acids could be separated from the leaves of sugar beet including [¹⁴C]alanine, γ-[¹⁴C]aminobutyric acid, [¹⁴C]glutamic acid, [¹⁴C]aspartic acid, [¹⁴C]serine, [¹⁴C]valine, and [¹⁴C]aspargine with specific activities of several microcuries per millimole. The specific activities of the products could be significantly increased by increasing the specific activity of the radioactive carbonate initially used.     

Glycosylation of Bovine Serum Albumin with D-[<Superscript>14</Superscript>C]-Glucose

Certain parameters of the Maillard reaction between bovine serum albumin (BSA) and D-[¹⁴C]-glucose were investigated.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 275–277, May–June, 2005.     

Biosynthesis of cytochalasans. Part 4. The mode of incorporation of common naturally-occurring carboxylic acids into cytochalasin D1.

Utilization of sodium [1-¹⁴C]-, [2–¹⁴C]-, and [1,2-¹³C]-acetates, [1-¹⁴C]-, [1-¹³C]-, or [2-¹⁴C]-propionates, [1-¹⁴C]-or [2-¹⁴C]-malonates, of [1-¹⁴C]- or of [1-¹⁴C]-myristic acid, or of [1-¹⁴C]- and [1-¹⁴C]-palmitic acid in the biosynthesis of cytochalasin D ( 1 ) by Zygosporium masonii was determined by degradation studies or by carbon magnetic resonance spectroscopy. The precursors were incorporated primarily via the acetate-malonate pathway to generate 1 from nine intact acetate units, eight of which are coupled in a head to tail fashion to form the C₁₆-polyketide moiety.     

Tracer studies on dinoflagellate luciferin with [N]-glycine and [N]-l-glutamic acid in the dinoflagellate Pyrocystis lunula

The bioluminescence of dinoflagellate is a typical luciferin-luciferase reaction. To clarify the biosynthesis of dinoflagellate luciferin, we performed a feeding experiment with [¹⁵N]-glycine and [¹⁵N]-l-glutamic acid in the dinoflagellate Pyrocystis lunula. In a control experiment, we also examined whether or not chlorophyll a was incorporated with these labeled compounds. We detected by mass spectrometry the incorporation of [¹⁵N]-glycine and [¹⁵N]-l-glutamic acid into the four tetrapyrrole rings of the luciferin. In the control experiment, chlorophyll a was also incorporated with [¹⁵N]-glycine and [¹⁵N]-l-glutamic acid. Our results show that either glycine or glutamic acid could be the original component of dinoflagellate luciferin as well as chlorophyll a in the dinoflagellate P. lunula.     

Synthesis of (methylchlorosilyl)methyldichlorophosphines

(Methylchlorosilyl)methyldichlorophosphines have been synthesized by the reaction of [dimethy(diethylamino)silyl]- or [methyl-bis(diethylamino)silyl]methylmagnesium chlorides with PCl₃ in ether at –40÷–20 °C and subsequent treatment of the reaction mixture with dry HCl. The structures of the compounds thus obtained have been studied by³¹P,¹H, and¹³C NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 989–990, May, 1993.     

On the biosynthesis of dendrolasin, a body constituent of the ant Lasius fuliginosus Latr

By feeding the ant Lasius fuliginosus LATR . with [¹⁴C]-1-acetate, [¹⁴C]-2-acetate, [¹⁴C]-2-mevalonate, [¹⁴C]-2-mevalonate, [¹⁴C]-1-glucose and [¹⁴C]-U-glucose, incorporation ratios of 10^?4 – 0,15% were obtained in the sesquiterpenoid dendrolasin. It was shown by analysis of the labelling pattern in dendrolasin that the insertions were spread over the whole molecule in exactly the manner that would be expected from terpene biosynthesis.     

Biosyntheis of the alkaloids of Ammodendron karelinii

Summary The biosynthesis of the alkaloids ofAmmodendron karelinii Fisch. et Mey has been studied by feeding the plant with labelled [1,5-¹⁴C]cadaverine. It has been shown that cadaverine is a precursor of anagyrine, pachycarpine, ammodendrine, N-methylcytisine, and cytisine. Possible routes of interconversions have been considered by feeding the plant with the tritium-labelled [³H]pachycarpine, [³H]lupanine, [³H]anagyrine, and [³H]ammodendrine.V. I. Lenin Tashkent State University. Institute of Plant Biochemistry, Academy of Sciences of the GDR, Halle. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 247–250, March–April, 1977.     

New synthesis of [8-arginine] vasopressin and its de-9-glycine analogs

A unified scheme is proposed for the synthesis of [8-arginine]vasopressin (I), de-9-glycine[8-arginine]vasopressin (II), and de-9-glycinamide[8-arginine]vasopressin (III) which has been developed on the basis of the tetrapeptide Gln-Asn-Cys(Bzl)-Pro and other homologous fragments of neurohypophyseal hormones as common initial and intermediate compounds. The free dithiols obtained by the reduction of protected derivatives of (I)–(III) by sodium in liquid ammonia have been oxidized to the corresponding cyclic disulfides (I)–(III) with the aid of 1 M H₂O₂ at 0–5°C and pH 8.5. The vasopressor activities of (I)–(III) are, respectively 470 ± 20, 1.7, and 0.5 IU/mg (rat, in vivo).Institute of Organic Synthesis, Latvian SSR Academy of Sciences, Riga. Translated from Khimiya Prirodnykh Soedinenii, No.3, pp. 433–439, May–June, 1988.     

Stereochemistry of planarchiral compounds,part X

2,7-Dibromo-1,6-methano[10]anulene (3) and 2,9-Dibromo-syn-1,6:8,13-diimino[14]anulene (9) were quantitatively separated into their enantiomers by chromatography on triacetylcellulose (TAC) in ethanol. X-ray structure analysis (Bijvoet technique) established the chiralities (+)(R)-3 and (+)(S)-9 for the dextrorotatory enantiomers.Comparison of the CD spectra allowed the configurational assignment to further optically active [10] and [14] anulenes which were also accessible by chromatography onTAC. Conversion of (+)(R)-2-bromo-1,6-methano[10]anulene (2) into the corresponding methylester (–)-4 confirmed its previously proposed chirality (–)(R).2,7-Dibromo-1,6-oxido[10]anulene (7) and 2,9-dibromo-syn-diimino[14]anulene (9) are in contrast to the 2,9-dibromo-syn-dioxido[14]anulene (10) optically stable until 250°C. Consequently their inversion barriers are higher than 42 kcal (176 kJ) mol^–1.The CD spectra of mono and disubstituted anulenes (with C₁ and C₂ symmetry, resp.) are compared: For the [10]anulenes theCotton effect around 330 nm seems to be specific for their configuration with a positive effect indicating (S)-chirality and vice versa. Some regularities concerning the chromatographic resolutions are discussed.

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Stereochemie planar chialer Verbindungen, 10. Mitt.: Röntgenkristallstruktur und absolute Chiralität überbrückter [10]- und [14] Anulene

Zusammenfassung 2,7-Dibrom-1,6-methano[10]anulen (3) und 2,9-Dibrom-syn-1,6:8,13-diimino[14]anulen (9) wurden durch Chromatographie an Triacetylcellulose (TAC) in Ethanol quantitativ in ihre Enantiomeren getrennt. Röntgenstruktur-analyse (Bijvoet-Technik) bewies für die rechtsdrehenden Enantiomeren die Chiralität (+)(R)-3 bzw. (+)(S)-9.Ein Vergleich der CD-Spektren ermöglichte die Konfigurationszuordnung weiterer optisch aktiver [10]- und [14]Anulene, die gleichfalls durch Chromato-graphie anTAC erhalten worden waren. Umwandlung von (+)(R)-2-Brom-1,6-methano[10]anulen (2) in den entsprechenden Methylester (–)-4 bestätigte dessen schon früher vorgeschlagene Chiralität (–)(R).Dibrom-1,6-oxido[10]anulen (7) und Dibrom-diimino[14]anulen (9) sind im Gegensatz zum Dioxido[14]anulen (10) bis 250°C optisch stabil. Ihre Inver-sionsbarrieren liegen somit über 42 kcal (176kJ) mol^–1.Die CD-Spektren von mono- und disubstituierten Anulenen (mit C₁ bzw. C₂-Symmetrie) werden verglichen: Für die [10]Anulene scheint derCottoneffekt um 330 nm konfigurationsspezifisch zu sein, wobei ein positiver Effekt (S)-Chiralität anzeigt — und vice versa. Einige Regelmäßigkeiten bezüglich der chromatographischen Enantiomerentrennung werden diskutiert.

     

The biosynthesis of laurifinine

The incorporation of (±)-nor-laudanosoline, (±)-N-nor-protosinomenine, (±)-N-nor-orientaline, (±)-N-nor-reticuline, and N-[2-(3-hydroxy-4-methoxyphenyl) ethyl]-2-(4'-hydroxyphenyl) ethylamine into laurifinine has been studied and the specific utilisation of the (±)-N-norprotosinomenine demonstrated. Double labelling experiments with (±)-[1-³H, 4'-methoxy-¹⁴C]-, and (±)-[1-³H, 7-methoxy-¹⁴C]-N-norprotosinomenines showed that 4' and 7, OMe groups and the H atom at the asymmetric centre of the precursor are retained in the bioconversion into laurifinine. Parallel experiments with (+)- and (-)-N-norprotosinomenine demonstrated specific utilisation of (+)-isomer into laurifinine.     

Carbon-14 kinetic isotope effect in the decarbonylation of lactic acid[1-14C]

The carbon-14 kinetic isotope effect for the decarbonylation of lactic acid[1-¹⁴C] in sulfuric acid has been measured in the temperature interval of 20–90°C. The experimental values of (k_12C/k_14C) are compared with the theoretical¹⁴C kinetic isotope effect calculated assuming that one carbon-oxygen stretching vibration is lost in the rate-determining step. The discrepancy between experimentally observed temperature dependence of the¹⁴C kinetic isotope effect and the theoretical one is explained by the possible side reactions which change the apparent degrees of decarbonylation and isotopic composition of CH₃CHOHCOOH[1-¹⁴C] used in experiments aiming at the determination of carbon-14 kinetic isotope effect in the decarbonylation process itself.     

Zur Biosynthese des Strychnins. 135. Mitteilung über Alkaloide

From the feeding of young plants of Strychnos nux-vomica with [¹⁴C]-1-and [¹⁴C]-2-acetate it could be deduced that the C-atoms 22 and 23 were derived from acetate. [¹⁴C]-2-mevalonate, [¹⁴C]-2-geraniol and [¹⁴C]-2-geranyl pyrophosphate were also incorporated into strychnine. The distribution of radioactivity in the «mevalonate-strychnine» was in agreement with the monoterpenoid hypothesis. Feeding experiments especially with [¹⁴C]-tryptophane showed that the main production centre of the alkaloid lay in the roots and that only a small part of it was carried to the leaves. Tritium labelled WIELAND GUMLICH aldehyde as well as N_(a)-[¹⁴C]-1-acetyl WIELAND GUMLICH aldehyde were not converted into strychnine by S. nux-vomica.     

Spezifisch14C-kernmarkierte Phenolderivate, 1. Mitt.: Synthese von [14C]-Guajacol

Zusammenfassung Für oxydative Abbauversuche wurden verschiedene spezifisch¹⁴C-kernmarkierte Phenolderivate benötigt. Guajacol, in verschiedenen Positionen des aromatischen Ringes markiert, wurde — teils von [1-¹⁴C]-Phenol, teils von [2-¹⁴C]-Aceton ausgehend — synthetisiert.

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Specifically¹⁴C-labelled phenol derivatives, I: Synthesis of [¹⁴C]guaiacol

Various phenol derivatives,¹⁴C-labelled in different specified positions of the aromatic ring, were required for oxidative degradation studies. Guaiacol, ring-labelled in different positions, was prepared both from [1-¹⁴C]phenol and from [2-¹⁴C]-acetone.

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Herrn Prof. Dr.M. Pailer zum 60. Geburtstag in Freundschaft gewidmet.     

Reactions of cyclic 1,3-dicarbonyl compounds with 1,2(1,4)-dihydro-1-methyl-2(4)-methylene-N-heterocycles. A new access to 6,12-methano-dibenz[d,g]-[1,3]oxazocinones

Summary The enamine-type methylene-N-heterocycles1–5 react with cyclic 2-ethoxymethylene-1,3-dicarbonyl compounds6 to give 2-[2-(hetarylidene)ethylidene]-1,3-dicarbonyl compounds7–14. The result of the reactions between 1,2-dihydro-1-methyl-2-methylene-quinoline (1a) and cyclic 1,3-dicarbonyl compounds depends on the nature of the dihydro intermediatesA/B. Dehydrogenation of keton intermediatesA results in 2-(1,2-dimethyl-4(1H)-quinolylidene)-1,3-dicarbonyl compounds17–21. Enol intermediatesB with 6-membered dicarbonyl ring form 6,12-methano-dibenz-[d,g][1,3]oxazocinones22–25.¹H NMR spectra and X-ray structure analysis prove the structure of23.

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Reaktionen cyclischer 1,3-Dicarbonylverbindungen mit 1,2(1,4)-Dihydro-1-methyl-2(4)-methylen-N-heterocyclen. Ein neuer Zugang zu 6,12-Methano- dibenz[d,g][1,3]oxazocinonen

Zusammenfassung Aufgrund ihres Enamincharakters reagieren die Methylen-N-heterocyclen1–5 mit cyclischen 2-Ethoxymethylen-1,3-dicarbonylverbindungen6 zu den 2-[2-(Hetaryliden)ethyliden]-1,3-dicarbonylverbindungen7–14. Das Ergebnis der Reaktionen zwischen 1,2-Dihydro-1-methyl-2-methylen-chinolin (1a) und cyclischen 1,3-Dicarbonylverbindungen hängt von der Natur der zwischenzeitlich entstehenden DihydroverbindungenA/B ab. Die Intermediat-KetoneA gehen durch Dehydrierung während der Reaktion in die 2-(1,2-Dimethyl-4(1H)chinolyliden)-1,3-dicarbonylverbindungen17–21 über. Die Intermediat-EnoleB mit sechsgliedrigem Dicarbonylring bilden in intramolekularer Reaktion die 6,12-Methano-dibenz[d,g][1,3]oxazocinone22–25, deren Struktur am Beispiel der Verbindung23 durch¹H-NMR sowie durch Röntgenkristallstrukturanalyse bewiesen wird.

     

13C NMR spectrum of coumarin

Summary The positions of the signals from the C₃, C₅, C₆, and C₇ carbon atoms in the¹³C NMR spectrum of coumarin have been established with the aid of information obtained from the¹³C NMR spectra of [3-D]-, [4-D]-, and 7-methoxycoumarins and by the use of an additive calculation based on the increments of the methoxy group in the¹³C NMR spectrum of anisole.M. V. Lomonosov Moscow State University Scientific-Research Institute of Pharmacology, Academy of Medical Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 458–462, July–August, 1975.