Reactions of Elemental Phosphorus and Phosphine with Electrophiles in Superbasic Systems: XV. Phosphorylation of Allyl Halides with Elemental Phosphorus

Elemental phosphorus (red or white) reacts with allyl chloride and allyl bromide in a two-phase system aqueous KOH-organic solvent to form tertiary symmetrical and mixed phosphine oxides among which tris(prop-2-enyl)-, bis(prop-2-enyl)[(E)-prop-1-enyl]-, bis(prop-2-enyl)[(Z)-prop-1-enyl]-, (prop-2-enyl)[(E)-prop-1-enyl][(Z)-prop-1-enyl]-, bis[(E)-prop-1-enyl](prop-2-enyl)-, bis[(Z)-prop-1-enyl](prop-2-enyl)-, tris-[(E)-prop-1-enyl]-, and bis[(E)-prop-1-enyl][(Z)-prop-1-enyl]phosphine oxides were identified. The conditions (room temperature, 60% aqueous KOH-dioxane) allowing preparation from white phosphorus and allyl bromide of tris(prop-2-enyl)- and bis(prop-2-enyl)[(E)-prop-1-enyl]phosphine oxides as major products in the total yield of up to 96% were found.     

Chemical composition and antimicrobial activity of the essential oil of Anthemis altissima L. var. altissima

The essential oil obtained from the flowering parts of Anthemis altissima L. var. altissima was analysed by gas chromatography and gas chromatography mass spectroscopy. In this study, 34 compounds representing 98.76% of the essential oil were identified. The main components were α-terpineol (26.42%), β-pinene (9.23%), cis-chrysanthenyl acetate (6.30%), globulol (5.36%), n-tricosane (4.41%), terpinen-4-ol (4.08%) and 1,8 cineole (3.84%). Antibacterial activities of the essential oil and its two major components (α-terpineol and β-pinene) were determined using microdilution method against both Gram-positive (Staphylococcus aureus, Bacillus subtilis, Staphylococcus epidermidis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa, Klebsiella pneumoniae) bacteria. The essential oil showed a broad-spectrum antibacterial activity (MICs ranged from 3.13 to 6.25?μL?mL(-1)). It was found that α-terpineol with minimum inhibitory concentration (MIC) values of the range 0.87-1.56?μL?mL(-1) was a more potent antibacterial agent than β-pinene with MIC values of the range 1.56-6.25?μL?mL(-1). All of them, the essential oil, β-pinene and α-terpineol, were more effective against Gram-positive bacteria than Gram-negative ones.     

The essential oils of the aerial parts of two Hypericum taxa (Hypericum triquetrifolium and Hypericum aviculariifolium subsp. depilatum var. depilatum (Clusiaceae)) from Turkey

In this study, essential oil compositions of two Hypericum L. taxa (Hypericum triquetrifolium Turra. and Hypericum aviculariifolium Jaub. et Spach subsp. depilatum var. depilatum (Freyn et Bornm.) Robson) naturally grown in Turkey were determined using gas chromatography and gas chromatography-mass spectrometry systems. The essential oils were obtained by hydrodistillation from the aerial parts of plants. A total of 45 compounds were identified in the essential oils of H. triquetrifolium; 1-hexanal (18.8%), 3-methylnonane (12.5%) and α-pinene (12.3%). In this study, 41 components were identified in H. aviculariifolium subsp. depilatum var. depilatum oil; α-pinene (52.1%), germacrene D (8.5%) and β-pinene (3.6%) were the predominant constituents. The essential oil analysis showed that monoterpene concentrations were higher than that of the sesquiterpenes in both oils. The results were discussed in the meaning of the usefulness of these plants and their chemicals as natural products and potential usage in chemotaxonomy.     

Volatile constituents of Amomum maximum Roxb and Amomum microcarpum C. F. Liang & D. Fang: two Zingiberaceae grown in Vietnam

The chemical composition of essential oils obtained from the hydrodistillation of different parts of Amomum maximum Roxb and Amomum muricarpum C. F. Liang & D. Fang (Zingiberaceae) grown in Vietnam are reported. The analysis was performed by means of gas chromatography–flame ionisation detectoorand gas chromatography coupled with mass spectrometry. The major compounds identified in the oils of A. maximum were β-pinene (20.4–40.8%), α-pinene (6.8–15.0%), β-elemene (2.5–12.8%) and β-caryophyllene (2.3–10.3%). Moreover, β-phellandrene (11.6%) was present in the root oil. The main compound identified in all the oil samples of A. muricarpum was α-pinene (24.1–54.7%) and β-pinene (9.2–25.9%). In addition, limonene (7.4%) and δ-3-carene (9.4%) were present in the leaves and stem oils, respectively. However, while β-phellandrene (8.3%) could be seen prominent in the root oil, the fruits contained significant amount of zingiberene (6.3%). The largest amount of τ-muurolol (13.0%) was found in the flower oil.     

Synthesis of acyclic bis-vinyl pyrimidines: a general route to d4T via metathesis

Unsaturated acyclic pyrimidine analogues, 1-{1-[1-(hydroxymethyl)prop-2-enyloxy]prop-2-enyl}uracil, 1-{1-[1-(hydroxymethyl)prop-2-enyloxy]prop-2-enyl}thymine and 1-{1-[1-(hydroxymethyl)prop-2-enyloxy]prop-2-enyl}cytosine having two asymmetric carbon atoms have been prepared in good yield starting from uridine and 5-methyluridine. The bis-vinyl thymine derivative underwent ring closure metathesis to give d4T, thus providing a novel synthesis of this compound.     

蒙古蒿精油化学成份的研究I.

The chemical constituents of the essential oil from the leaves of artemisia mongolica Fisch. were separated by gas chromatography employing glass capillary eolumns and identified by GC-MS-COM. 30 components have been separated and identified, i.e. 2-methyl-2-butene, methylene cyclopentane, 7,7-dimethyl-3-methylen-bicyclo-(3, 1, 1) heptane, α-thujene, α-pinene, camphene, 1-octen-3-o1, β-thujene, β-pinene, α-phellandrene, bornylene, p-cymene, terpinen-1-o1, artemisia ketone, γ-terpinene, β-terpineol, 3,7,7-trimethyl-bicyclo-(3, 1,1)-2-heptanol, α-terpinolene, verbenone, linalool iso-thujone, thujone, camphor, isopulegone, isoborneol, terpinen-4-o1, α-terpineol, myrtenol, trans- carveol, cis-carveol.     

Three new diterpenes and the biological activity of different extracts of Jasonia montana

Three new diterpenes, namely jasonin-a (1), jasonin-b (2), and jasonin-c (3) were isolated from the aerial parts of Jasonia montana (Asteraceae). Their structures were elucidated on the basis of spectral data as [(1E)-2-((2S)-1,2,5-trimethylbicyclo[3.2.l]octan-8-yl)vinyl] benzene-3-carboxylic acid (1), [3-((2S, 5S)-1,2, 5-trimethylcycloheptanyl)propyl]benzene-3-carboxylic acid (2), and [(1E)-3-((7R)-1,7-dimethy-4-methylenecycloheptanyl)prop-1-enyl] benzene-3-carboxylic acid (3). In addition, the previously reported 5,7,3'-trihydroxy-3,6,4'-trimethoxy flavone designated as centaureidin (4), was also isolated and characterized from this source. The different extracts of the plant were also screened for hypoglycemic, antidiabetic, and antimicrobial activities, wherein the petroleum ether and ethanolic extracts exhibited hypoglycemic and antidiabetic activity, and the petroleum ether and chloroform extracts showed antimicrobial activity.     

Synthese von Plectranthonen,diterpenoiden Phenanthren-1,4-chinonen

Synthesis of Plectranthons, Diterpenoid Phenanthrene-1,4-diones The following phenanthrene-1,4-diones have been synthesized by using the photocyclization of the corresponding highly substituted stilbenes as the key step: 3-hydroxy-5,7,8-trimethyl-2-(prop-2-enyl)phenanthrene-1,4-dione ( 1 ), (RS)-, (R)-, and (S)-2-[3-hydroxy-5,7,8-trimethyl-1,4-dioxophenanthren-2-yl]-1-methylethyl acetate ( 2 , 31 , and 32 , resp.), 3-hydroxy-7,8-dimethyl-2-(prop-2-enyl)phenanthrene-1,4-dione ( 3 ), 3-hydroxy-7,8,10-tri-methyl-2-(prop-2-enyl)phenanthrene-1,4-dione ( 4 ), 5,7,8-trimethyl-2-(prop-2-enyl)phenanthrene-1,4-dione ( 17 ), and 3-hydroxy-2-methylphenanthrene-1,4-dione ( 42 ). The quinones 1 and 3 proved to be identical with the recently isolated plectranthons A and C. Compounds 2 , 31 , and 32 exhibited the same UV/VIS, IR, ¹H-NMR and mass spectra as natural plectranthon B , but had different melting points. This might be due either to crystal modifications or to diastereoisomerism caused by the helical structure of the phenanthrene-1,4-dione skeleton. The spectral data of synthetic 4 were not compatible with those of natural plectranthon D for which structure 4 had been proposed based mainly on ¹H-NMR arguments concerning the chemical shifts of H? C(9) and H? C(10) in 1–3. Extensive ¹H-NMR investigations have now revealed that the currently stated assignments of the H? C(9)/ H? C(10) AB system have to be reversed for highly substituted phenanthrene-1,4-diones: in the model compounds 2-methylphenanthrene-1,4-dione (41) and 2, H? C(10) resonates al lower field as expected (peri-position), whereas in the highly substituted congeners 1 , 2 , 3 , 31 , and 32 , H? C(9) is shifted paramagnetically, a fact which had lead to the erroneous assignment of structure 4 for natural plectranthon D .     

An unusual reaction of propargylamines with CH2I2 and Et3Al

N-{2-[(1-R-Cyclopropyl)methyl]prop-2-enyl}-N,N-dimethylamines were prepared in 80-90% yields by the reaction (5 h, 23-25 C) of propargylamines R-C=C-CH₂NMe₂ (where R = alkyl, Ph) with a system of reactants CH2I2-Et₃Al taken in the molar ratio [propargylamine]: [Et₃Al]: [CH₂I₂] = 1: 6: 6. In the case of phenyl-substituted propargyl- amine, N-({1-[(1-phenylcyclopropyl)methyl]cyclopropyl}methyl)-N,N-dimethylamine is selectively formed in 76% yield upon the elongation of the reaction time to 4 days.     

The preparation and reactions of 1,3,4,5,6,7,8-heptafluoro-2-naphthyl prop-2-enyl ether: Formation of 1,3,4,5,6,7,8-heptafluoro-1-(prop-2-enyl)naphthalen-2-one and the photolysis and pyrolysis of this ketone [1].

1,3,4,5,6,7,8-Heptafluoro-2-naphthyl prop-2-enyl ether (8) was isomerised in boiling xylene to 1,3,4,5,6,7,8-heptafluoro- 1-(prop-2-enyl)naphthalen-2-one (9). Photolysis of (9) gave 2,5,7-trifluoro-3,4-(tetrafluorobenzo)tricyclo[3.3.1.O^2,7]non-3- en-6-one (11) (by a [2 + 2] addition) and 1,2,7-trifluoro-3,4- (tetrafluorobenzo) tricyclo [3.3.1.O^2,7]non-3-en-8-one (12) (via an initial [3,5] photochemically-allowed sigmatropic shift). Pyrolysis of (9) at 455° also gave (11), while at 490°, both (9) and (11) gave 1-fluorovinyl 4,5,6,7,8-pentafluoro-1-naphthyl ketone (19).     

Chemical composition and herbicidal activity of the essential oil from a Cistus ladanifer L. population from Spain

The essential oil composition of Cistus ladanifer grown in central Spain was analysed by gas chromatography and gas chromatography/mass spectrometry, revealing it to be rich in oxygenated compounds, with trans-pinocarveol (20.00%), bornyl acetate (7.03%) and terpinen-4-ol (6.37%) as the main monoterpene compounds. Viridiflorol (13.59%) and ledol (4.36%) were the main constituents of the oxygenated sesquiterpene fraction. Large amounts of α-pinene (4.70%) were found in the hydrocarbonated fractions. To study its possible use as a natural herbicide, the oil was tested in?vitro against Amaranthus hybridus, Portulaca oleracea, Chenopodium album, Conyza canadensis and Parietaria judaica, completely inhibiting A. hybridus germination, and nearly blocking C. canadensis and P. judaica germination at all concentrations assayed. In P. oleracea, the oil showed less effect, inhibiting its germination at the higher doses studied. It did not control C. album germination. Regarding seedling length, the oil had strong phytotoxic activity, being effective at all concentrations tested.     

The Effects of Antioxidants on the Changes in Volatile Compounds in Heated Welsh Onions (Allium fistulosum L.) during Storage

Welsh onion (Allium fistulosum L.) is usually used to enhance the flavor characteristics of various foods. Volatile compounds in Welsh onions, including sulfur-containing compounds, may vary during heat process and storage. Accordingly, the changes in the volatile compounds in Welsh onions, subjected to heat and antioxidant (ascorbic acid and glutathione) treatments during storage, are investigated in the present study. The majority of sulfur-containing compounds in Welsh onions showed significant differences between the untreated Welsh onions and heated Welsh onions. During the heating of the Welsh onions, some sulfur-containing compounds, such as 2-methylthiirane, 1-(methyldisulfanyl)prop-1-ene, 1-[[(E)-prop-1-enyl]disulfanyl]propane, 1-(propyltrisulfanyl)propane, 1-[[(E)-prop-1-enyl]trisulfanyl]propane, and (methyltetrasulfanyl)methane, showed significant differences between the untreated and heated Welsh onions (p < 0.05). In addition, partial least square discriminant analysis (PLS-DA) was applied to discriminate the heated Welsh onion samples added with different antioxidants. The heated Welsh onion samples added with ascorbic acid was mainly associated with 2-phenylacetaldehyde, acetic acid, methylsulfanylmethane, prop-2-ene-1-thiol, undecan-2-one, and (2E,4E)-deca-2,4-dienal. Moreover, the key volatile compounds in the heated Welsh onion samples added with glutathione were 3-ethylthiophene, 1-(methyldisulfanyl)-1-methylsulfanylpropane, 1-methylsulfanylpentane, 2-prop-2-enylsulfanylpropane, and 1-propan-2-ylsulfanylbutane.     

Chemical investigation of the essential oil from berries and needles of common juniper (Juniperus communis L.) growing wild in Estonia

The essential oils obtained by simultaneous distillation and extraction (SDE) from the fresh and dried needles and dried berries of Juniperus communis L. of Estonian origin were subjected to GC-FID and GC-MS analyses. The yields of the oils ranged between 0.2% and 0.6% from juniper berries and between 0.5% and 1.0% from needles (dried weight). A total of 87 compounds were identified, representing over 95% of the oil. The major compounds in the needle oil were monoterpenes α-pinene (33.3-45.6%), sabinene (0.2-15.4%), limonene (2.8-4.6%) and sesquiterpenes (E)-β-caryophyllene (0.8-10.3%), α-humulene (0.8-6.2%) and germacrene D (3.0-7.8%). The juniper berry oil was rich in α-pinene (53.6-62.3%), β-myrcene (6.5-6.9%) and germacrene D (4.5-6.1%). The main oxygenated terpenoids found in the needle oil were germacrene D-4-ol (0.4-4.0%) and α-cadinol (to 2.7%). The oil from fresh needles contained high amounts of (E)-2-hexenal (3.7-11.7%).     

Antiangiogenic polyketides from Peperomia dindygulensis Miq

Two new polyketides: 2Z-(heptadec-12-enyl)-4-hydroxy-3,4,7,8-tetrahydro-2H-chromen-5(6H)-one (1) and 2-(heptadec-12-enyl)-5-hydroxy-5,6,7,8-tetrahydrochromen- 4-one (2), together with eleven known compounds: 4-hydroxy-2-[(3,4-methylenedioxy- phenyl)tridecanoyl] cyclohexane-1,3-dione (3), oleiferinone (4), 4-hydroxy-2-[(3,4- methylenedioxyphenyl)undecanoyl]cyclohexane-1,3-dione (5), 4-hydroxy-2-[(11-phenyl- undecanoyl)cyclohexane-1,3-dione (6), proctorione C (7), surinone C (8), 5-hydroxy- 7,8,4'-trimethoxyflavone (9), 5-hydroxy-7,8,3',4'-tetramethoxyflavone (10), 5-hydroxy- 7,3',4'-trimethoxyflavone (11), 5,8-dihydroxy-7,3',4'-trimethoxyflavone (12) and cepharanone B (13) were isolated from the whole plant of Peperomia dindygulensis Miq. Their structures were elucidated by spectroscopic methods, including 2D-NMR techniques. Compounds 2, 3, 5 and 8 inhibited human umbilical vein endothelial cell (HUVEC) proliferation and compounds 5 and 8 sharply suppressed HUVEC tube formation.     

Methyl and Phenylmethyl 2-Acetyl-3-{[2-(dimethylamino)-1-(methoxycarbonyl)ethenyl]amino}prop-2-enoate in the Synthesis of heterocyclic systems: Preparation of 3-amino-4H-pyrido-[1,2-a]pyrimidin-4-ones

Methyl 2-acetyl-3-{[2-(dimethylamino)-1-(methoxycarbonyl)ethenyl]amino}prop-2-enoate ( 4 ) and phenyl-methyl 2-acetyl-3-{[2-(dimethylamino)-1(methoxycarbonyl)ethenyl]amino}prop-2-enoate ( 5 ) were prepared in three steps from the corresponding acetoacetic esters, and used as reagents for the preparation of N³-protected 3-amino-4H-pyrido[1,2-a]pyrimidin-4-ones 10 – 12 , 5H-thiazolo[3,2-a]pyrimidin-5-one 13 , 4H-pyrido[1,2-a]-pyridin-4-one 19 and 2H-1-benzopyran-2-ones 20 – 23 . Free 3-amino-4H-pyrido[1,2-a]pyrimidin-4-ones 24 – 26 were prepared from 10 – 12 by removal of the 2-(methoxycarbonyl)-3-oxobut-1-enyl or 3-oxo-2-[(phenyl-methoxy)carbonyl]but-1-envl as N-protecting group by various methods.     

Synthesis,Crystal Structure and Biological Activity of 2-[(Pyridin-2-yl)methylthio]-1H-benzimidazole Derivatives

In order to discover the novel anti-tumor agents, a series of 2-[(pyridin-2-yl)methylthio]-1 H-benzimidazole derivatives were designed and synthesized, and the structures were characterized by IR, MS, and proton NMR. 2-[(3,4-Dimethoxypyridin-2-yl)methylthio]-1 Hbenzimidazole was investigated with X-ray crystallography, and the molecule is in orthorhombic system, space group P212121, with a = 9.1828(16), b = 11.625(2), c = 13.463(2) ?, Z = 4, R = 0.0231 and wR = 0.0596. The antitumor activities of target compounds were evaluated against human liver cancer cell line HepG2, and human liver normal cell line HL7702 using MTT assay. The target compounds have demonstrated weak or moderate anti-tumor activity against HepG2, while all the target compounds exhibit no cytotoxic effects on HL7702.     

Studies on the constituents of Broussonetia species X. Six new alkaloids from Broussonetia kazinoki Sieb.

Six new alkaloids, broussonetines W, X, M1, U1, J3, and J2 (1-6) were isolated from the branches of Broussonetia kazinoki SIEB. (Moraceae) as minor constituents. They were formulated as (2R,3R,4R,5R)-2-hydroxy-methyl-3,4-dihydroxy-5-17-(cyclohexy-2-on-1(6)-enyl)heptyllpyrrolidine (1), (2R,3S,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-17-(cyclohexy-2-on-1(6)-enyl)heptyl]pyrrolidine-4-O-beta-D-glucopyranoside (2), (2R,3R,4R,5R)-2-hydroxymethyl-3,4-dihydroxy-5-[(9R)-9,13-dihydroxytridecyl]- pyrrolidine (3), (2S,3S,4S)-2-hydroxymethyl-3,4-dihydroxy-5-(10-oxo-13-hydroxytridecyl)-5- pyrroline (4), (2R)-2-[(IS,2S)-1,2-dihydroxy-8-1(2R,3R,4R,5R)-5-(2-hydroxymethyl-3,4-dihydroxy-1-acetylpyrrolidinyl)loctyl]piperidine (5), (2R)-2-[(1S,2S)-1,2-dihydroxy-8-[(2R,3R, 4R,5R)-5-(2-hydroxymethy]-3,4-dihydroxypyrrolidinyl)]octyl]piperidine (6).     

Comparative analysis of the composition of essential oils and supercritical carbon dioxide extracts from the berries and needles of Estonian juniper (Juniperus communis L.)

The composition of the volatile oil of the common juniper (Juniperus communis L.) from Estonia was analyzed by gas chromatography (GC-FID) and gas chromatography-mass spectrometry (GC-MS). The yield and composition of the oil obtained by different methods (micro-distillation and extraction, SDE, and supercritical carbon dioxide extraction, SFE) from various parts of juniper (berries, needles) were compared. The oil yield ranged from 0.7 to 2.1%. The content of α-pinene of juniper-berry essential oil was 47.9, that of juniper needleoil, 36.4%. The oil yields and composition obtained by SDE and SFE from juniper needles were similar. The oil obtained by SFE from juniper berries contained more sesquiterpenes and high boiling compounds than that obtained by SDE.     

Chemical composition and In vitro antioxidant and antidiabetic activities of Eucalyptus Camaldulensis Dehnh. essential oil

The present study was designed to determine the composition of the essential oil of Eucalyptus camaldulensis Dehnh. leaves and to examine its in vitro antioxidant and antidiabetic activities. The chemical composition of the essential oil from Eucalyptus camaldulensis Dehnh. leaves was analyzed by GC/GC-MS, twenty-nine compounds representing 99.10% of the total oil were identified. The major components of the oil were p-cymene (68.43%), 1,8-cineole (13.92%), 1-(S)-α-pinene (3.45%) and R-(+)- limonene (2.84%). The antioxidant features of the essential oil were evaluated using inhibition of 2,2-diphenyl-1-picrylhydrazyl, hydroxyl, and superoxide radicals, inhibition of hydrogen peroxide and lipid peroxidation assays. We also studied α-amylase and α-glucosidase inhibition in vitro to assess the antidiabetic properties of the essential oil. Both α-amylase and α-glucosidase were inhibited by a non-competitive mechanism.     

2，6-二-O-乙氧乙基-3-O-三氟乙酰基-β-环糊精气相色谱手性固定相的制备及应用

将β-环糊精的2,6-位引入乙氧乙基,3-位引入三氟乙酰基,合成了新的环糊精衍生物2,6-二-O-乙氧乙基-3-O-三氟乙酰基-β-环糊精,并采用静态法涂渍毛细管气相色谱柱,考察了毛细管柱的柱性能和分离性能。结果表明,该固定相对G rob试剂、苯的二取代位置异构体氯甲苯、硝基甲苯和溴甲苯以及10种手性化合物如α-取代丙酸酯化合物、1-(2′-硝基苯基)-乙醇、α-甲基-对氯苯乙腈和丙炔醇酮乙酸酯等具有良好的分离效果。其中,对α-甲磺酰基丙酸酯对映体的拆分效果最好;对α-取代丙酸的甲酯衍生物的分离效果优于乙酯衍生物;对α-羟基取代丙酸酯的分离效果优于α-卤代丙酸酯。