珠子参化学成分分析

从珠子参根茎中分离得到7个化合物. 利用核磁共振、 质谱和红外等手段, 并结合其理化性质, 鉴定了其结构, 它们分别是24(R)-珠子参苷R1, 6-O-[β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-[β-D-吡喃葡萄糖基(1→4)-β-D-吡喃葡萄糖基]-20(S)-原人参三醇、 6″-乙酰基-人参皂苷Rd、 人参皂苷Rf、 竹节参皂苷Ⅳa、 人参皂苷Rd和竹节参皂苷Ⅴ. 其中, 24(R)-珠子参苷R1和6-O-[β-D-吡喃葡萄糖基(1→2)-β-D-吡喃葡萄糖基]-20-O-[β-D-吡喃葡萄糖基(1→4)-β-D-吡喃葡萄糖基]-20(S)-原人参三醇为2个新化合物, 6″-乙酰基-人参皂苷Rd 和人参皂苷Rf为首次从珠子参根茎中得到.     

Thermal decomposition of basic aluminium potassium sulphate. Part I. Stages of decomposition

The stages of thermal decomposition of basic aluminium potassium sulphate were studied with the use of differential thermal analysis (DTA), thermogravimetry (TG), mass spectrometry (MS), IR spectroscopy (IR), and X-ray diffraction phase analysis (XRD). The individual stages of the decomposition were determined and both solid and gaseous products of the dissociation were identified. On the basis of spectrometric data and thermodynamic calculations the possibility of the occurrence of the SO in the gaseous reaction products is discussed.     

Comparative essential oil composition of aerial parts of Tanacetum dumosum Boiss. from Southern Zagros,Iran.

The essential oils of leaves and flowers of Tanacetum dumosum Boiss., an endemic medicinal shrub, were extracted by using hydrodistillation method and analysed using GC and GC–MS. A total of 43 and 44 compounds were identified in the essential oils from the leaves and flowers of T. dumosum, respectively. The major chemical constituents of leaves oil were borneol (27.9%), bornyl acetate (18.4%), 1,8-cineol (17.5%), α-terpineol (5.3%), cis-chrysanthenyl acetate (3.3%), camphene (2.7%) and terpinene-4-ol (1.9%), while the main components of the flower oil were isobornyl-2-methyl butanoate (41.1%), trans-linalyl oxide acetate (11.9%), 1,8-cineole (7.7%), thymol (4.2%), linalool (3.9%), camphor (2.9%), isobornyl propanoate (2.9%), α-terpineol (2.1%) and caryophyllene oxide (2.0%). Major qualitative and quantitative variations for some main chemical compounds among different aerial parts of T. dumosum were identified. High contents of borneol, bornyl acetate, 1,8-cineol and linalool in the leaves and flowers of T. dumosum show its potential for use in the food and perfumery industry.     

Investigation of phenanthridone and dioxotetrahydrodiazapyrene. 4. Synthesis of amino-substituted phenanthridones and dioxotetrahydrodiazapyrenes

The corresponding mono-, di-, and triamino derivatives substituted in the 2, 4, and 8 positions of the phenanthridone ring were obtained by reduction of mono-, di-, and trinitro-substituted phenanthridone (I), phenanthridone-10-carboxylic acid (II), phenanthridone-1-carboxylic acid (III), 4H-cyclopenta[k,l,m]phenanthridine-5,9-dione (IV), 4H-cyclopenta[k,l,m]phenanthridin-5-one (V), 5,10-dioxo-4,5,9,10-tetrahydro-4,9-diazapyrene (VI), and 5,9-dioxo-4,5,9,10-tetrahydro-4,10-diazapyrene (VII) with powdered iron in an electrolyte medium, with hydrogen in the presence of a nickel catalyst, or with stannous chloride. The 2,4,7,9-tetraamino derivative of VI was similarly obtained. 1-Amino-, 7-amino-, and 10-amino-phenanthridones were obtained by the Schmidt reaction from the corresponding carboxylic acids. 1,10-Diamino-, and 3,8-diaminophenanthridones were similarly obtained from the corresponding aminofluorenones.See [1] for Communication 3.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 394–397, March, 1981.     

Volatile components of Centaurea bracteata and C. pannonica subsp. pannonica growing wild in Croatia

This paper reports on the volatile components of oils from the aerial parts (CBA) and roots (CBR) of Centaurea bracteata Scop. and aerial parts of C. pannonica (Heuffel) Simonkai subsp. pannonica (CPA), two Asteraceae growing wild in Croatia. The volatile components, obtained by hydrodistillation, were determined by GC-MS analysis. The yields (w/w) of the dried oils were 0.10% (CBA), 0.22% (CBR) and 0.09% (CPA), respectively. A total of 91 compounds were identified accounting for 91.1%, 93.3% and 87.9% of the total oil for CBA, CBR and CPA, respectively. All the samples were characterized mainly by hydrocarbons (7.1-34.1%), fatty acids (9.7-45.9%), and oxygenated sesquiterpenes (15.2-16.6%). The major components of the samples were hexadecanoic acid (8.1-31.1%), nonacosane (0.6-13.4%) and caryophyllene oxide (4.5-11.9%). Monoterpenes, both hydrocarbons and oxygenated, were either absent or present in low amounts in all the oils. The similarity in the oil contents is consistent with the two species being placed in the same section, Jacea.     

Structure-property relationships of copolyamides. I. Thermal properties and crystallization

Six nylon salts [hexamethylenediammonium adipate (6.6), hexamethylenediammonium terephthalate (6.T), hexamethylenediammonium isophthalate (6.I), p-xylylenediammonium adipate (PXD.6), m-xylylenediammonium adipate (MXD.6), and m-xylylenediammonium isophthalate (MXD.I)] were copolymerized with ε-caprolactam. The resulting random copolyamides showed different modes of crystallization as confirmed by the melting temperature depression and the decrease in the isothermal crystallization rate. By selective hydrolysis it was found that the differences in T_m depression and isothermal crystallization rate were due to partial inclusion of comonomers in the crystal lattice. The effect of comonomer structure on the crystallization rate is also discussed.     

Antiproliferative activity of Luehea candicans Mart. et Zucc. (Tiliaceae)

Luehea candicans Mart. et Zucc. (Tiliaceae) is known as 'a?oita-cavalo' and is one of the most important medicinal plants found in the Brazilian cerrado. The crude methanolic extracts of the branches and leaves and their fractions were evaluated using the following cancer cell lines: MCF-7 (breast), NCI-ADR (breast expressing the multidrug resistance phenotype), NCI-460 (lung), UACC-62 (melanoma), 786-0 (kidney), OVCAR (ovarian), PCO-3 (prostate), HT-29 (colon) and K-562 (leukaemia). The crude methanolic extracts from the branches (B) and leaves (L) were able to inhibit the growth of the K-562 and 786-0 cell lines in a dose-dependent manner, with GI(50) values of 8.1 and 5.4 μg mL(-1), respectively. The hexane (L1), chloroform (L2) and methanol (L4) fractions derived from extract L showed a high selectivity and pronounced cytostatic activity against 786-0 (GI(50) ~ 40 μg mL(-1)). A significant amount of lupeol was isolated from fraction L2. The chloroform (B2) and methanol (B3) fractions derived from extract (B) exhibited less selectivity, showing the highest cytostatic activity against K-562, NCI-ADR, OVCAR, MCF-7 and NCI-460 cells, with GI(50) values between 27 and 40 μg mL(-1). Lupeol, betulin, a mixture of steroids, (-)-epicatechin, vitexin and liriodendrin were isolated from these active fractions.     

Metabolism of terniary compounds. V. Decomposition of diincarbonic acids and hydrocarbons in vivo

10,12-Heneicosadiynoic acid (I), 5,7-hexadecadiynoic acid (IV), and 10,12-docosadiynedioic acid (VI) were fed to rats. As metabolites 4,6-undecadiynedioic acid (II), 5,7-dodecadiynedioic acid (V), and 4,6-decadiynedioic acid (VII) respectively were isolated from the urine. 10,12-Heptadecadiynoic acid (III) also yielded metabolite II. Furthermore 9,11-eicosadiyne (X) and for comparison purposes eicosane (XI), hexadecanedioic acid (VIII), and docosanedioic acid (IX) were fed. X and XI were incorporated into depot fat and liver lipids to a cetain degree. The diynes I, II, IV, and X are new compounds.     

Novel copolymers of styrene. 8. Phenoxy ring-substituted butyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, phenoxy ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂C₄H₉ (where R is 2-(4-chlorophenoxy), 3-(4-chlorophenoxy), 4-(3-chlorophenoxy), 4-(4-chlorophenoxy), 4-(4-fluorophenoxy), 2-(3-methoxyphenoxy), 2-(4-methoxyphenoxy), 3-(4-methoxyphenoxy), 4-(4-methoxyphenoxy), 3-(4-methylphenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (3.1-6.5% wt), which then decomposed in the 500-800°C range.     

The volatile constituents analysis of Eremostachys macrophylla Montbr. & Auch. from Iran

The volatile constituents of the aerial parts of Eremostachys macrophylla growing in the wild in Iran have been examined by GC-FID and GC-MS. Altogether, 16 compounds were identified, constituting approximately 96.4% of the oil. The oil of E. macrophylla consisted mainly of germacrene-D (47.1%), germacrene-B (17.8%), gamma-elemene (9.1%), myrcene (6.7%), beta-elemene (2.7%), and beta-phellandrene (2.6%).     

Two New Chemical Constituents of Veratrum dahuricum (Turcz.) Loes. f.

Two new chemical constituents, one new steroid, neoveratrenone ( 1 ), and one new glycerol ester, 1‐[11‐(ferulyloxy)undecanoyl)]glycerol ( 2 ), were isolated and characterized from the roots and rhizomes of Veratrum dahuricum (Turcz .) Loes . f., together with five known compounds, i.e., hexacosanoic acid 2,3‐dihydroxypropyl ester ( 3 ), syringaresinol ( 4 ), prosapogenin A of dioscin ( 5 ), verapatulin ( 6 ), and oxyresveratrol ( 7 ). Their structures were established by extensive analysis of spectroscopic data as well as by comparison with literature reports. The compounds were evaluated for cytotoxic activity against three tumor cell lines of HepG‐2, HeLa, and K562/S.     

Chemical composition of the essential oil of Salvia multicaulis Vahl. var. simplicifolia Boiss. growing wild in Lebanon

The essential oil of aerial parts of Salvia multicaulis Vahl. var. simplicifolia Boiss. (Lamiaceae) growing wild in Lebanon was obtained by hydrodistillation and was analysed by GC and GC-MS. 67 compounds constituting 95.2% of the oil were identified, the major components being alpha-copaene (8.0%), alpha-pinene (6.6%), myrtenol (5.7%), trans-sabinyl acetate (5.3%).     

Adamantylazoles. 5. The molecular structure of 1-(1-adamantyl)pyrazoles

The crystal structures of 1-(1-adamantyl)-3,5-dimethylpyrazole 1 and 1-(1-adamantyl)-3,4,5-trimethylpyrazole 2 were studied by X-ray analysis. The space groups and cell parameters are: 1 , Cc, 13.4452(4), 14.9407(4), 7.1119(2) Å, 90, 111.944(2), 90°, with Z = 4. 2, P2₁/c, 6.7466(1), 21.2565(7), 10.1462(2) Å, 90, 106.368(2), 90°, with Z = 4. The final disagreement factors were 0.069 and 0.061, for 721 [2σ(I)] and 1950 [2σ(I)] observed reflexions, respectively. Compound 1 presents the adamantyl residue disordered between the two usual conformations. The experimental dipole moments and the carbon-13 chemical shifts (both in hexadeuteriodi-methylsulfoxide and in the solid state) were measured and discussed in connection with the structure of these compounds.     

Chemical constituents of the new endophytic fungus Mycosphaerella sp. nov. and their anti-parasitic activity

Chemical investigation of a new endophytic fungus, Mycosphaerella sp. nov. strain F2140, associated with the foliage of the plant Psychotria horizontalis (Rubiaceae) in Panama, resulted in the isolation of cercosporin (1) and a new cercosporin analog (3) as the major components. The structures of minor compounds in the extract were elucidated by detailed spectroscopic analysis as 2-(2-butyl)-6-ethyl-3-hydroxy-6-methylcyclohex-2-ene-1,5-dione (4), 3-(2-butyl)-6-ethyl-5-hydroxy-2-methoxy-6-methyl-cyclohex-2-enone (5), and an isomer of 5 (6). To study the influence of the hydroxy groups on the anti-parasitic activity of cercosporin, compound 1 was acetylated to obtain derivative 2. The isolated compounds 1- 6 were tested in vitro to determine their anti-parasitic activity against the causal agents of malaria (Plasmodium falciparum), leishmaniasis (Leishmania donovani), and Chagas disease (Trypanosoma cruzi). Cytotoxicity and potential anticancer activity of these compounds were evaluated using mammalian Vero cells and MCF7 cancer cell lines, respectively. Compounds 1 and 2 displayed high potency against L. donovani (IC50 0.46 and 0.64 microM), T. cruzi (IC50 1.08 and 0.78 microM), P. falciparum (IC50 1.03 and 2.99 microM), and MCF7 cancer cell lines (IC50 4.68 and 3.56 microM). Compounds 3-6 were not active in these assays at a concentration of 10 microg/mL.     

Phenolic constituents of licorice. VIII. Structures of glicophenone and glicoisoflavanone, and effects of licorice phenolics on methicillin-resistant Staphylococcus aureus

Two new phenolic compounds, glicophenone (1) and glicoisoflavanone (2), were isolated from commercial licorice, and their structures were elucidated on the basis of spectroscopic data. Antibacterial assays of licorice phenolics for Staphylococcus aureus, including four strains of methicillin-resistant S. aureus (MRSA), and also for Escherichia coli K12 and Pseudomonas aeruginosa PAO1, were then examined. Two compounds among them, 8-(gamma,gamma-dimethylallyl)-wighteone (21) and 3'-(gamma,gamma-dimethylallyl)-kievitone (28), showed remarkable antibacterial effects [minimum inhibitory concentrations (MICs), 8 microg/ml on the MRSA strains and methicillin-sensitive S. aureus. Licochalcone A (14), gancaonin G (20), isoangustone A (24), glyasperins C (30) and D (31), glabridin, (32), licoricidin (33), glycycoumarin (34) and licocoumarone (40) showed antibacterial effects on the MRSA strains with MIC values of 16 microg/ml. Effects on the beta-lactam resistance of the MRSA strains were also examined, and licoricidin (33) noticeably decreased the resistance of the MRSA strains against oxacillin, as shown by the reduction in the MICs of oxacillin (lower than 1/128-1/1000 in the presence of 8 microg/ml of 33, and 1/8-1/32 in the presence of 4 microg/ml of 33). Mechanistic study suggested that 33 does not inhibit the formation of penicillin-binding protein 2' (PBP2'), but affects the enzymatic function of PBP2'.     

Aryloxy acetic acid diuretics with uricosuric activity. I. Polycyclic aryloxy acetic acids.

In order to obtain lead compounds for uricosuric diuretics, various polycyclic aryloxy acetic acids [isoindole derivative (7), quinazoline derivative (15), benzopyran derivative (20), xanthone derivative (24), benzofuran derivative (30) and indene derivative (36)] were prepared. These compounds were evaluated for diuretic activity in rats, uricosuric activity in rats and antihypertensive activity in 11-deoxycorticosterone acetate (DOCA)/salt hypertensive rats. Among the compounds, 20 showed potent diuretic, uricosuric and moderate antihypertensive activities. Therefore, we selected 20 as a lead compound for development of new uricosuric diuretics.     

The pregnane derivatives of the roots from Asclepias lilacina Weimarck. II. Structure determination

Partial formulae have been derived for the nine lilacinosides which were isolated, partly in pure form, and for two related substances which were only obtained as a mixture. These substances are derived basically from two pregnane derivatives (sarcostin and deacetyl-metaplexigenin) present in partially benzoylated form. Of these were isolated genin B = 12,20-di-O-benzoyl-sarcostin ( 1 ), genin C = 12-O-benzoyl-20-O-acetylsarcostin ( 2 ), and genin D, which could be identified with 12-mono-O-benzoyl-desacetyl-metaplexigenin ( 4 ). These three genins are bound to different sugars, the latter being present as mono-, di-, tri- and probably tetra-saccharides. The structures of these were partially derived: after mild hydrolysis three new disaccharides were obtained, which are named asclepobiose (U1), lilacinobiose (U2) and digalilobiose (U5). U1 and U2 were isolated in crystalline form. On hydrolysis U1 yielded 3-O-methyl-6-deoxy-D-allose (U3), U2 yielded 3-O-methyl-6-deoxyglucose (thevetose), and digitalose was obtained from U5.     

Chemical composition of the essential oil of Pelargonium quercetorum Agnew. of Iran

The volatile constituents in the essential oil of Pelargonium quercetorum Agnew., growing wild in Kurdistan, Iran were investigated through GC and GC/MS technique. Twenty-six compounds, representing 21 (80.77%) of the total oil were identified. The main components were: alpha-pinene (25.28%), alpha-fenchyl acetate (20.63%), limonene (9.94%), beta-caryophyllene (8.20%), camphene (4.31%), delta-cadinene (3.32%), beta-pinene (3.21%), alpha-amorphene (2.80%), valencene (2.73%), ledene (2.25%) and p-cymene (1.63%).     

Analysis of essential oils from Scutellaria orientalis ssp. alpina and S. utriculata by GC and GC-MS

The chemical composition of the essential oils obtained from aerial parts of Scutellaria orientalis L. ssp. alpina (Boiss.) O. Schwarz and S. utriculata Labill. growing wild in Lebanon, were analyzed by GC and GC-MS. In S. orientalis ssp. alpina, strongly characterized by sesquiterpenes (41.2%) and particularly sesquiterpene hydrocarbons (31.7%), hexahydrofarnesylacetone (11.7%) was recognized as the main constituent, together with hexadecanoic acid (7.6%), caryophyllene (7.4%), caryophyllene oxide (6.8%), 4-vinylguaiacol (5.4%) and germacrene D (5.4%). S. utriculata oil was instead constituted above all by monoterpenes (42.2%), particularly oxygen containing monoterpenes (39.9%), and in this oil the main compounds were linalool (20.1%), 4-vinyl guaiacol (15.5%), alpha-terpineol (8.9%), (E)-nerolidol (8.9%) and geraniol (8.2%).     

Polymerizations of substituted cyclopropanes. I. Radical polymerization of 1,1-disubstituted 2-vinylcyclopropanes

Diethyl 2-vinylcyclopropane-1,1-dicarboxylate (Ia), 2-vinylcyclopropane-1,1-dicarbonitrile (Ib), ethyl 1-cyano-2-vinylcyclopropanecarboxylate (Ic), and 1,1-diphenyl-2-vinylcyclopropane (Id) were radically homo- and copolymerized. Ia, Ib, and Ic polymerized cleanly in 1,5-type ring-opening fashion to yield polymers of high molecular weight. Id failed to homopolymerize but copolymerized with common monomers which included maleic anhydride. Infrared (IR) spectra indicated that the double bonds of the polymer chains were in trans form. All polymers were soluble in solvents and solution-cast films were clear and flexible, showing T_g values in the 25–40°C range. Model reactions of those monomers with benzenethiol also indicated predominant 1,5-addition reactions. From the results of our investigation it was concluded that the driving force for the facile radical 1,5-polymerization of Ia, Ib, and Ic was the stabilization of growing radicals by two substituents.