Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.     

Resin acids of the oleoresins of conifers growing in Transcarpathia

The chemical composition of the resin acids of the oleoresins of five species of the conifers of Transcarpathia has been studied. The oleoresins contain eight resin acids. ^8,9-Isopimaric and anticopalic acids have been found in the acid part of the oleoresin of the Weymouth pine.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 212–214, March–April, 1987.     

Gas-chromatographic determination of the composition of the volatile components of the oleoresins of some species of conifers

Using the method of analytical GLC in a glass capillary column, the compositions have been studied of the volatile fractions of the oleoresins of five species of conifers:Larix decidua,Pinus strobus,Pinus mugo,Picea excelsa, andPinus abies. In the oleoresins 21 monoterpene and 22 sesquiterpene compounds were identified from their relative retention times and with the aid of additives. The main components of the volatile fractions of the oleoresins were - and -pinenes and 3-carene among the monoterpenes, and longifolene caryophyllene, - and -cadinenes and -murolene among the sesquiterpene compounds. The quantitative analysis of the fractions was carried out by the method of internal normalization from averaged correlation coefficients.Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 629–632, September–October, 1990.     

Gas-chromatographic determination of the composition of the volatile components of the oleoresins of some species of conifers

Using the method of analytical GLC in a glass capillary column, the compositions have been studied of the volatile fractions of the oleoresins of five species of conifers:Larix decidua,Pinus strobus,Pinus mugo,Picea excelsa, andPinus abies. In the oleoresins 21 monoterpene and 22 sesquiterpene compounds were identified from their relative retention times and with the aid of additives. The main components of the volatile fractions of the oleoresins were α- and β-pinenes and 3-carene among the monoterpenes, and longifolene caryophyllene, δ- and γ-cadinenes and α-murolene among the sesquiterpene compounds. The quantitative analysis of the fractions was carried out by the method of internal normalization from averaged correlation coefficients.     

Dichotellides A-E, five new iodine-containing briarane type diterpenoids from Dichotella gemmacea

Five new briarane type diterpenoids, dichotellides A−E (1−5), were isolated from the South China Sea gorgonian Dichotella gemmacea together with four known analogues (6−9). Compounds 1−5 represent the first examples of iodine-containing briarane type diterpenoids from nature. The structures of these diterpenoids were elucidated by spectroscopic analysis, including 1D, 2D-NMR, and HRESIMS, and the absolute configuration of 1 was further confirmed by single crystal X-ray diffraction analysis. All the isolates were evaluated for cytotoxicity activity against four human tumor cell lines, and only 3 exhibited marginal activity against SW1990 (human pancreatic cancer).     

Complete 13C NMR assignments for ent-kaurane diterpenoids from Sideritis species

In this work, the detailed NMR studies and full (13)C NMR assignments for five diterpenoids isolated from Sideritis caesarea and Sideritis athoa are described. The assignments are based on a combination of 1D and 2D NMR techniques including (1)H, (13)C, (1)H-(1)H COSY, gHSQC [(1)J(C,H)] and gHMBCδ(C) [(n)J(C,H)(n=2 and 3)] and NOESY experiments.     

Flow rate gradient high-speed counter-current chromatography separation of five diterpenoids from Triperygium wilfordii and scale-up

In this paper, high-speed counter-current chromatography (HSCCC) instruments with different gravitational forces were applied for the separation of bioactive compounds from Triperygium wilfordii Hook.f. The critical parameters including sample concentration, sample volume and flow rate were first optimized on an analytical Mini-DE HSCCC system, and then scaled up to a preparative TBE 300A HSCCC system. Although this scale-up process was performed using different CCC instruments with different centrifuges and gravitational forces, the same resolutions were obtained and the elution time could be predictable. Five diterpenoid compounds and one unknown compound were separated from Triperygium wilfordii Hook.f. by HSCCC with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (HEMW) (3:2:3:2, v/v/v/v). This one-step flow gradient separation produced triptonide (25 mg), isoneotriptophenolide (77 mg), hypolide (83 mg), unknown compound (1 mg), triptophenolide (42 mg), triptonoterpene methyl ether VI (37 mg) from 320 mg crude extract with purities of 98.2%, 96.6%, 98.1%, 95.3%, 95.1%, and 96.5%, respectively. Their purities and structures were identified by high-performance liquid chromatography, mass spectrometry and NMR. This paper demonstrates that analytical CCC plays an important role in optimizing parameters and scale-up process when analytical CCC and preparative CCC are supplied by different manufacturers with different gravitational forces, and the scale-up process from analytical CCC to preparative CCC is still predictable.     

Complete assignments of the 1H and 13C NMR spectra of five rearranged abietane diterpenoids

An NMR study of five highly functionalized and rearranged abietane diterpenoids is described. In addition to 1D NMR methods, including 1D NOESY spectra, 2D shift‐correlated experiments [¹H, ¹³C‐gHSQC‐¹J (C,H) and ¹H, ¹³C‐gHMBC‐ⁿJ (C,H) (n = 2 and 3)] were used for the complete and unambiguous ¹H and ¹³C chemical shift assignments of these substances. Copyright © 2002 John Wiley & Sons, Ltd.     

New ent-kaurene-type diterpenoids possessing cytotoxicity from the New Zealand liverwort Jungermannia species

Two new ent-kaurene-type and a new rearranged ent-kaurene-type diterpenoids possessing cytotoxicity against a human leukemia cell line have been isolated from the New Zealand liverwort Jungermannia species, together with previously known ent-kaurene-type diterpenoids. Their structures were established based on extensive NMR techniques.     

Neutral species from "non-protic" N-heterocyclic ionic liquids

Possible isomerisation of 1,2,3-trialkylimidazolium and 1-alkylpyridinium ion pairs by proton transfer and by the nucleophilic addition of the anion to the cation have been investigated at the B3LYP/6-31+G* and B3LYP/6-311+G** levels of density functional theory. The deprotonation energies of 1,2,3-trialkylimidazolium and 1-alkylpyridinium cations to diaza-pentafulvene and pyridinium-ylide, respectively, were only slightly larger than that of 1,3-dialkylimidazolium salts yielding N-heterocyclic carbenes. Accordingly, in the case of 1,2,3-dialkylimidazolium salt ion pairs the stability of the H-bonded complex between the fulvene and the corresponding acid can be comparable to that of the ion pair in the presence of sufficiently basic anions, such as acetate. In the case of the pyridinium salts the nucleophilicity of the cation dominates over the acidity, and the formation of 1,2- or 1,4-dihydropyridine derivatives is preferred over proton transfer.     

Novel cytotoxic kaurane-type diterpenoids from the New Zealand Liverwort Jungermannia species

Novel cytotoxic rearranged kaurene- and ent-kaurene-type diterpenoids against HL-60 cells have been isolated from the unidentified New Zealand liverwort Jungermannia species together with previously known ent-kaurane-type diterpenoids. Their structures were determined by extensive NMR techniques, chemical degradation and X-ray crystallographic analysis.     

Negombins A-I, new chlorinated polyfunctional diterpenoids from the marine sponge Negombata species

Nine novel compounds designated negombins A-I (1-9) were isolated, together with latrunculin, from the Tanzanian sponge Negombata sp. The nine are sacculatane type diterpenes, previously only known from liverworts. The structures of the compounds were elucidated by interpretation of MS and 1D and 2D NMR spectra. A possible biogenesis initiated by the naturally rare chloronium ion is suggested, possibly hinting to a guest microorganism as the source of the compounds. Compound 4 is toxic to brine shrimp larvae.     

Seed oils of five species of the family Rosaceae

Summary Some physicochemical characteristics of the seed oils of five species of plants of the family Rosaceae have been studied, confirming the information on the fatty-acid compositions of these oils that we obtained by the GLC, TLC, and PC methods. It has been shown that a high content of linolenic acid is characteristic for each of the five seed oils of herbaceous plants of this family.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 491–493, July–August, 1977.     

Terpenoids of the oleoresins ofPinus pityusa andP. eldarica

The chemical composition of the oleoresins of the pinesPinus pityusa andP. eldarica growing in the Caucasus has been studied. In relation to the amounts of the main components, the oleoresins of these species are similar. Characteristic for their resins is a high content of caryophyllene. Diterpenoids are represented mainly by tricyclic compounds, among which pimarinol and isopimarinol and methyl 15-hydroxydehydroabietate predominate.     

Comparative affinity chromatography of acetylcholinesterases from five vertebrate species

The efficacy of N-methylacridinium affinity chromatography in the purification of acetylcholinesterases from chicken, rat, calf and human brain and from the electric organ of the electric fish Torpedo marmorata has been investigated. Retention of the enzymes on the N-methylacridinium columns exceeded 90% in all instances except for the chicken enzyme, where 40-80% retention was observed depending on the acridinium concentration. Sucrose density gradient centrifugation profiles revealed no difference between the distribution of molecular forms in the crude extracts and in the partially purified fractions eluted from the columns by decamethonium iodide.     

Biological activity of bicyclic and tricyclic diterpenoids from Salvia species of immediate pharmacological and pharmaceutical interest

Diterpenoids are a class of compounds that derive from the condensation of four isoprene units that leads to a wide variety of complex chemical structures, including acyclic bi-, tri-and tetra-cyclic compounds; in Salvia species, only bi-, tri-and tetra-cyclic compounds have been found. This review covers a wide range of biological activities and mode of action of diterpenoids isolated from Salvia species that might raise some pharmacological and pharmaceutical interest. We have produced a synoptic table where the biological activities of the main active principles are summarized. Our analysis emphasizes that diterpenoids from Salvia species continue to be a plant defence system since their antimicrobic activity. Experimental studies show that most of diterpenoids considered have cytotoxic and/or antiproliferative activity. Some of them have also cardiovascular and central effects. In a less extended manner, diterpenoids from Salvia species show gastrointestinal, urinary, antinflammatory, antidiabetic, ipolipidemic and antiaggregating effects. In the last decade, several clinical trials have been developed in order to investigate the real value of Salvia extracts treatment; results obtained are promising and confer scientific basis in the use of medicinal plants from folk medicine.