O. I. Sal’nikova

Neutral Constituents of Chamaenerion angustifolium Leaves

The constituent composition of the unsaponified residue from the lipophilic extract of Chamaenerion angustifolium leaves was studied. A total of 92 neutral compounds including triterpenoids, polyprenols, and dolichols were identified using GC-MS and HPLC methods. Greater than 80 compounds were observed for the first time in this plant.

Components of the ethylacetate extract of Hedysarum theinum roots

Isoflavonoids (-)-medicarpin, (-)-vestitol, and formononetin and butylphenols raspberry ketone and rhododendrol were isolated for the first time from the ethylacetate extract of Hedysarum thienum roots by column chromatography. GC-MS showed that the ethylacetate extract contained fatty acids, the principal ones being palmitic, linoleic, oleic, behenic, and lignocerinic.

COMPARATIVE ANALYSIS OF ESSENTIAL OIL COMPOSITIONS FROM LEAVES AND STEMS OF Rhododendron adamsii, R. aureum, AND R. dauricum

Chemical compositions of essential oils (EO) from leaves and stems of Rhododendron adamsii, R. aureum, and R. dauricum were studied by GC/MS. The analysis demonstrated that the EO of these plants contained mainly mono-and diterpene hydrocarbons. A large amount of alkanes was also found in the EO of R. aureum.

Reaction of polyfluorinated chalcones with guanidine

Reactions of polyfluorinated chalcones with guanidine in the presence of bases are accompanied by elimination of the polyfluorophenyl group. 3-(Pentafluorophenyl)-1-phenylprop-2-en-1-one and its derivatives reacted with guanidine under basic conditions to give 4-phenylpyrimidin-2-amine, polyfluorobenzenes, and Michael adducts, 3-(2-amino-4-phenylpyrimidin-5-yl)-3-(4-R-2,3,5,6-tetrafluorophenyl)-1-phenylpropan-1-ones. 1-(Pentafluorophenyl)-3-phenylprop-2-en-1-one and 1,3-bis(pentafluorophenyl)prop-2-en-1-one were converted into cinnamic acid derivatives whose reaction with guanidine afforded 2-amino-6-aryl-5,6-dihydropyrimidin-4(1H)-ones.

Isolation of pomolic acid from Chamaenerion angustifolium and the evaluation of its potential genotoxicity in bacterial test systems

The lipophilic components of the medicinal plant, the fireweed (Chamaenerion angustifolium), have been examined using the raw materials of a three-year harvest. Twenty eight aliphatic and six triterpene acids have been detected for the first time by chromatography—mass spectrometry analysis. It has been shown using the Ames test and the SOS chromotest that pomolic acid possesses no genotoxic and mutagenic properties.

Lipophilic Constituents from Malus baccata

Fruit of Malus domestica is the most well-known and utilized fruit. The history of apple cultivation covers about 50 centuries. The chemical composition of apples is widely studied because of their beneficial effect on the human body. Apples contain large amounts of both simple and complex carbohydrates [1]. Bioflavonoids, phenolic acids, vitamins, and trace elements are responsible for the principal biological activities [1, 2]. Apple peel was reported to have a high content of triterpene acids, which could also be responsible for biological activity [3, 4]. Constituents with high antioxidant activity such as anthocyans, procyanidins, dihydrochalcones, quercetin in the free and glycosylated states, epicatechin, and chlorogenic acid were observed in apple peel, pulp, and juice [1, 5]. However, wild species and apple hybrids are practically unstudied despite their high biological activity [6]. Thus, apple wax, which contains bound aliphatic and free triterpene acids and is spread over the surface, occurred in greater quantities per unit mass in fruit of poorer-bearing plants. The content of triterpene acids in apple peel reached 4 mg per cm2 of surface [3, 7]. We analyzed neutral and acidic constituents of lipophilic compounds extracted in three ways from fruit of Malus baccata L., the chemical composition of which is little studied [6, 8]. In the first instance, epicuticular wax from fruit was investigated; in the second, ground pulp with peel (seeds were not studied); in the third, ground fruit after removing epicuticular wax. Equal weights (100 g of fresh fruit) were covered with methyl-t-butylether and extracted with vigorous stirring at 50°C. The procedure was repeated four times (4 150 mL). The extracts were separated using saponification into neutral and acidic constituents. The acidic constituents were converted to methyl esters using diazomethane. Neutral constituents were analyzed without derivatization as before [9]. GC-MS spectra were recorded on a Hewlett–Packard G 1800 A instrument consisting of an HP 5890 series II gas chromatograph, an HP 5971 mass-selective detector, and a column (30 m 0.25 mm 0.25 m) of HP-5MS (5% diphenyl, 95% dimethylsiloxane). The carrier gas was He (1 mL/min). The column temperature was held at 50°C for 2 min, increased at 4°C/min to 300°C, and held for 30 min at 300°C. The vaporizer temperature was 280°C; ion source, 170°C. Aliphatic acids and alcohols, sterols, triterpene alcohols, and ursolic and oleanolic acid methyl esters were found in the neutral part. The acidic part contained previously observed compounds [8], saturated constituents with chain lengths 24–30, and triterpene acids, which were isolated from M. domestica but were not previously observed in M. baccata. Their total content in the acidic part was >50%. The principal constituents were ursolic, oleanolic, and pomolic acids. Tables 1 and 2 list the constituent ratios. Ursonic, oleanonic, acetylursolic, acetyloleanolic, pomonic, corosolic, and maslinic acids were detected in trace quantities. The results indicated that M. baccata could provide a source of biologically active constituents including triterpene acids and could be incorporated into diet food owing to the low sugar content.

Non-Volatile Compounds of Needles, Trimmed Saplings, and Outer Bark of Pinus densiflora

Pinus densiflora Siebold et Zucc. (Pinaceae) is a woody plant that forms forests in Korea, Japan, northeastern China, and the extreme south of the Russian Far East. Preparations of its needles are used in Korea to treat scurvy, arthritis, hypertension, and dyspepsia [1, 2] and as tonics [3]. Commercially important products from this pine are the sap, turpentine, and essential oil, which exhibit bactericidal properties [4] and are also used in aroma therapy and as ingredients of diuretic and expectorant phototherapeutic compositions [2]. The composition of essential oils from needles and cones were thoroughly studied [4–7]. Kim and Shin [6] studied the composition of monoand sesquiterpenoids in the petroleum-ether extract of pine needles. However, the highly volatile components made up only an insignificant part of the lipophilic extracted substances [8]. Also, literature data on non-volatile extracted substances from P. densiflora are limited. The goal of the present work was to compare the little studied non-volatile lipophilic constituents of needles (N), trimmed saplings (T), and outer bark (B) of P. densiflora from a single natural population using GC-MS. The distribution of the studied compounds in the sapling system of P. densiflora was interesting from a practical point of view and for the chemotaxonomy of the genus Pinus. We neglected losses of highly volatile constituents during work up of the extracts because the yields of extracted substances from various parts of the pine sapling system exceeded the essential oil contents in them [8]. Dried needles (N), trimmed saplings (T), and outer bark (B) of P. densiflora were extracted exhaustively with hexane. The yields of the extracts were 5.0% from N, 9.4% from T, and 1.1% from B of the dry raw material mass. The yield of extracted lipophilic substances from N was significantly greater than that reported earlier from its essential oil (0.3% of fresh raw material) [7]. The maximum yield (9.4%) of extracted substances was obtained from T; the minimum (1.1%), from B. Table 1 presents the obtained extracts and their contents. Similar yields of neutral compounds and free acids were obtained from the B extract whereas the yields of acids were ~3 times greater than that of neutral compounds for extracts of N and T (Table 1). Fractionation of the B extract isolated a waxy substance that was insoluble in t-BuOMe and aqueous NaOH solution and consisted apparently of suberic-type oligomers [9]. Saponification of the neutral compounds produced acids and unsaponified neutral compounds, the yields of which are given in Table 1. The amount of acids formed upon saponification of the neutral compounds from B was greater than upon saponification of neutral compounds from N and T. This indicated that B contained more fats, waxes, and other esters in the extracted substances than N and T. Fractions of free acids (A), acids after saponification (S) as methyl esters, and unsaponified neutral compounds (U) were analyzed by GC-MS. Tables 2 and 3 present the compositions of fractions A and U, respectively. The principal constituent of the acid fraction from the N extract (N-A) was trans-4-epi-communic acid (3, 43.6%). The contents of other major diterpene acids were significantly lower [dehydroabietic (6), 9.9%, and sandaracopimaric (2) acid, 6.1%). The total content of fatty acids was ~2%. The principal constituents in the analogous fraction from the T extract (T-A) were abietane-type acids [neoabietic (9), 16.5%; levopimaric (4) together with palustric (5), 15.4%; and dehydroabietic (6) acid, 14.4%].

Aliphatic and Terpene Constituents of Alcea nudiflora Extracts

The genus Alcea (Malvaceae) comprises 77 species, three of which [A. ryhticapa (Trautv) Iljin; A. nudiflora (Lindl.) Boiss.; and A. litvinovii Iljin] grow wild in Uzbekistan [1–3]; and three (A. nudiflora, A. kusariensis, and A. taurica), in Russia [4]. The chemical composition of A. nudiflora is insufficiently studied [4]. High contents of polyprenols are found in many plants of the family [5–8]. We studied previously the quantitative ratio of neutral bioactive constituents in the unsaponified part of the EtOH extract of A. nudiflora [8]. Cyclopropenic acids (CPA), which are absent in plants of most other families, are a chemotaxonomic marker of the family Malvaceae [9–11]. CPA are toxic and induce a shift in the fatty-acid composition of test animal tissues toward increased saturated constituents [12–14]. Therefore, the acid part of the extracts must be thoroughly investigated. The goal of the present study was to compare the compositions of aliphatic and terpene constituents isolated from the aerial part of A. nudiflora by solvents of different polarity, namely, EtOH and methyl-tert-butylether (MTBE). This extractant replaces Et2O for processing of plant raw material and provides a high degree of extraction of biologically active compounds [15]. The aerial part of A. nudiflora was collected in July 2013 in Namangan Oblast (Pap District, Sang village) during the start of fruiting and were characterized by the morphological features described in the literature [1–3]. Air-dried raw material was ground and extracted in a percolator by MTBE or EtOH. Sample preparation for HPLC and GC-MS included also a hydrolysis step as before [16]. The yields of extracts, acids, and unsaponified substances (US) from hydrolysis of A. nudiflora (mass% of raw material) were as follows:

Alkaloids from the New Species Papaver kuvajevii

A new Papaver species, P. kuvajevii Schaulo et Sonnikova, which is a rare species of the flora of western Sayan (relict, endemic), was discovered in 2003 at the Sayano-Shushenskii Natural Biosphere Reserve and described [1]. An investigation of the chemical composition of P. kuvajevii would prompt its industrial production while preserving the genetic resource of this natural endemic species if valuable biologically active constituents were found. The goal of the present work was to study the alkaloid composition of P. kuvajevii. Herein we communicate results from a GC-MS investigation of the alkaloid composition of this plant. Plant material (aerial part, stems, leaves, flowers, pods) was collected in July 2012 at Sayano-Shushenskii Natural Biosphere Reserve. Herbarium specimens are preserved at the Reserve Herbarium. The yield of substances from air-dried and ground aerial parts (285 g) that were extracted by EtOH in a Soxhlet apparatus was 12.6% (36.0 g). The EtOH extract was worked up with dilute H2SO4 and separated by fractional extraction into fractions according to basicity using the classical method [2]. Extraction by CHCl3 produced alkaloid fraction AC (36.9 mg, 0.01% relative to starting air-dried raw material) after basicification by Na2CO3 (pH 8) and alkaloid fraction B (83.8 mg, 0.03%) after basicification by NaOH (pH 11). The fractions were analyzed by GC-MS on an HP 5890 Series II GC with an HP 5971 mass-selective detector (EI, 70 eV) and HP-5 capillary column (5% diphenyl95% dimethylsiloxane, 30 m 0.25 mm, 0.25 m) using He carrier gas at 1 mL/min. The column temperature regime was 50°C (2 min), 50–300°C (10 °C/min), and 300°C (30 min). The vaporizer temperature was 280°C; ion-source, 170°C. The scan rate was 1.2 scan/s in mass range 29–650 amu. Constituents were identified by comparing total mass spectra with those in the NIST08 and W8N08 databases. The principal alkaloids in both fractions were amurensinine (1) and mecambridine (syn. oreophylline) (2). In addition to these, minor alkaloids amurensine (3) and -allocryptopine (4) were also identified (Table 1). Fraction AC was separated by preparative TLC on SiO2 F254 plates (Merck) using CHCl3–EtOH (15:1, v/v) to afford six fractions that were analyzed by GC-MS. Fractions AC-4 and AC-5 were enriched in amurensinine (1). Fraction B was also separated by preparative TLC under the same conditions and afforded seven fractions that were analyzed by GC-MS. Fraction B-3 was enriched in mecambridine (2); fraction B-5, 1. Fractions AC-4, AC-5, and B-5 were combined. PMR spectra of additionally purified 1 (2.3 mg, 0.00080%) and 2 (3.1 mg, 0.00108%) were recorded. The structures of isolated alkaloids 1 and 2 were confirmed by PMR spectral data and comparison with those reported [3, 4]. Amurensinine (1). 1Í NMR spectrum (400 MHz, CDCl3, , ppm): 6.77–6.54 (each 1H, s, H-1, 4, 7, 10), 5.96, 5.90 (2H, 2s, OCH2O), 4.07 (1H, m, H-6), 3.89 (3H, s, OCH3), 3.80 (3H, s, OCH3), 3.71 (1H, m, H-6), 3.68–3.66 (1H, m, H-11), 3.00 (1H, m, H-12), 2.94 (1H, m), 2.58 (3H, s, N-CH3). Mecambridine (2). 1Í NMR spectrum (400 MHz, CDCl3, , ppm): 6.62 (1H, s, H-9), 6.36 (1H, s, H-4), 5.91, 5.90 (2H, 2s, OCH2O), 4.70 (2H, s, CH2OH), 4.27–4.21 (1H, m, H-13a), 4.01 (3H, s, OCH3), 3.88 (3H, s, OCH3), 3.86 (3H, s, OCH3), 2.64–3.80 (8H, 2H-5, 6, 8, 13).

Studies of the Lipophilic Components of a Dense Extract of the Herb Alfredia Cernua and its Nootropic Properties

Chromato-mass spectrometry (GC/MS) studies of the chemical composition of a dense extract of the herb Alfredia cernua (L.) Cass. prepared by processing raw material with 95 % ethanol identified 31 aliphatic, including 2-hydroxy- and dicarboxylic, acids, three phenolcarboxylic acids, one di- and two triterpenoic acids, and 16 neutral lipophilic components. A total of 40 compounds were detected in Alfredia cernua for the first time. T maze experiments showed that the plant extract promoted changes in the motivational domain in normal animals, activating appetitive and consumatory behavior due to nootropic and anxiolytic actions, which were greater than those of piracetam.