New alkylamides from the pericarps of Zanthoxylum schinifolium.

The pericarps of Zanthoxylum schinifolium Sieb. et Zucc were called "green huajiao", which were used as traditional folk medicine and popular seasoning in China. In this study, twenty-seven alkylamides, including a rare alkylamide containing two amide groups (1), an alkylamide with a furan ring (5), six new alkylamide analogues (2-4, 6-8), together with nineteen known alkylamides (9-27) were isolated from green huajiao. Their structures were elucidated by extensive spectroscopic analysis, including 1D, 2D NMR, HRESIMS, and UV spectra. Furthermore, compounds 5, 18, 21, and 22 exhibited weak protective activity for corticosterone-induced PC12 cells damage.

Synthesis and biological evaluation of arylpyrazoles as fungicides against phytopathogenic fungi.

3-phenol-1H-pyrazoles (2), 4-halogeno-3-phenol-1H-pyrazoles (3) and 2-(1-phenol-1H-pyrazol-5-yl)phenols (4) were prepared by the condensation of (E)-3-(dimethylamino)-1-phenylprop-2-en-1-ones and hydrazine hydrate or phenylhydrazine in good yields. They were evaluated against five phytopathogens fungi, namely Cytospora sp., Colletotrichum gloeosporioides, Botrytis cinerea, Alternaria solani and Fusarium solani in vitro. Most of the above-mentioned compounds exhibited activities. For example, 4-chloro-2-(1H-pyrazol-3-yl)phenol (3k) and 4-bromo-3-phenol-1H-pyrazole (3b) showed good and broad-spectrum antifungal properties against Cytospora sp., C. gloeosporioides, Botrytis cinerea, Alternaria solani and F. Solani with [Formula: see text] values ranging from 4.66 to 12.47 [Formula: see text]g/mL. The results showed that pyrazoles with one aryl group at 3-position (2 and 3) exhibited better antibacterial activity than those with two aryl substituents (4). In addition, the existence of an electron-withdrawing group, a substituent on the ortho-position of phenol ring or a halogen atom at the 4-position of the pyrazole enhanced the antifungal activity of pyrazoles 2 and 3. A series of arylpyrazole derivatives was facilely prepared and was evaluated against five phytopathogens fungi including Cytospora sp., Colletotrichum gloeosporioides, Botrytis cinerea, Alternaria solani, and Fusarium solani in vitro. Most of those compounds exhibited remarkable antifungal activities and were superior to the positive control hymexazol.

Synthesis of pyrazolo[1,5-a]pyrimidine derivatives and their antifungal activities against phytopathogenic fungi in vitro.

5,6-Diarylpyrazolo[1,5-a]pyrimidines (3) and 6,7-diarylpyrazolo[1,5-a]pyrimidines (4) were chemoselectively synthesized by the condensation of isoflavone (1) and 3-aminopyrazole (2). 5,6-Diarylpyrazolo[1,5-a]pyrimidines (3) were obtained via microwave irradiation, and 6,7-diarylpyrazolo[1,5-a]pyrimidines (4) were obtained via conventional heating. In addition, the pyrimidine derivatives 3 and 4 were evaluated against five phytopathogenic fungi (Cytospora sp., Colletotrichum gloeosporioides, Botrytis cinerea, Alternaria solani, and Fusarium solani) using the mycelium growth rate method. Some of them were effective in inhibiting the growth of the five phytopathogenic fungi. For instance, 6,7-diarylpyrazolo[1,5-a]pyrimidines (4j) inhibited the growth of A. solani with an [Formula: see text] value of 17.11 [Formula: see text], and 6,7-diarylpyrazolo[1,5-a]pyrimidines (4h) inhibited the growth of both Cytospora sp. and F. solani with [Formula: see text] values of 27.32 and 21.04 [Formula: see text], respectively. A chemoselective synthesis of 5,6-pyrazolo[1,5-a]pyrimidines 3 derivatives in excellent yields was performed under microwave irradiation and 6,7-pyrazolo[1,5-a]pyrimidines 4 were also prepared using heating method. The antifungal properties of 3 and 4 were tested against Cytospora sp., Colletotrichum gloeosporioides, Botrytis cinerea, Alternaria solani, and Fusarium solani.

Fluoride-promoted cross-coupling of chloro(mono-, di-, or triphenyl)germanes with aryl halides in "moist" toluene. Multiple transfer of the phenyl group from organogermane substrates and comparison of the coupling efficiencies of chloro(phenyl)germanes with their corresponding stannane and silane counterparts.

The trichlorophenyl-, dichlorodiphenyl-, and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of tetrabutylammonium fluoride in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two, or three phenyl groups from the organogermanes. The corresponding chlorophenylstannanes were found to be more reactive than chlorophenylsilanes, which in turn were more effective than chlorophenylgermanes. One chloride ligand on the Ge or Si center allows efficient activation by fluoride to promote transfer of up to three aryl groups from germane or silicon. However, no haloligand was necessary to be present on the Sn center, since tetraphenyltin efficiently transferred up to four phenyl groups during fluoride-promoted couplings with aryl halides. (19)F NMR studies suggested formation of the fluorophenylgermanes and the hypervalent germanate species as possible intermediates.

One-step synthesis of diarylpyrazolo[3,4-b]pyridines from isoflavones.

A new concise, facile, and efficient method for the synthesis of 3-hydroxy-5,6-diphenylpyrazolo[3,4-b]pyridine derivatives has been described. The cyclocondensation of isoflavones with 3-amino-5-hydroxypyrazole in the presence of sodium methoxide gave fused heteroaromatic 3-hydroxy-5,6-diphenylpyrazolo[3,4-b]pyridines in moderate to good yields.

Arylchlorogermanes/TBAF/"moist" toluene: a promising combination for Pd-catalyzed Germyl-Stille cross-coupling.

The trichlorophenyl,- dichlorodiphenyl,- and chlorotriphenylgermanes undergo Pd-catalyzed cross-couplings with aryl bromides and iodides in the presence of TBAF in toluene with addition of the measured amount of water. One chloride ligand on the Ge center allows efficient activation by fluoride to promote transfer of one, two, or three phenyl groups from the organogermane precursors.

[Synthesis of 2-amino-4, 5-diarylpyrimidines and their protective effects against oxygen-glucose deprivation in PC12 cells].

A series of 6 novel 2-amino-4, 5-diarylpyrimidines were synthesized by the reaction of isoflavones with guanidine. They were identified by the spectra of IR, 1H NMR, 13C NMR and elemental analysis. The protective effects of 2-amino-4, 5-diarylpyrimidines against oxygen-glucose deprivation leading by sodium hydrosulfite in PC12 cells were studied by MTT method. It was shown that 2-amino-4, 5-diarylpyrimidines exhibited neuroprotective effects against oxygen-glucose deprivation injury in PC12 cells, which could increase the amount of survival PC12 cells and reduce their injured degree in the model.

Concise synthesis of 2, 3-diarylpyrimido[1,2-a]benzimidazole based on isoflavones.

The 2,3-diarylpyrimido[1,2-a]benzimidazole derivatives were prepared by one-step cyclocondensation of 2-aminobenzimidazole with isoflavone in methanol. Single-crystal diffraction analysis was performed for 2-(2-hydroxyl-4-isopropoxy-phenyl)-3-phenylpyrimido[1,2-a]benzimidazole. The fluorescence properties of the fused 2, 3-diarylpyrimido[1, 2-a]benzimidazole were evaluated.

One-pot synthesis of 4,5-biphenyl-2-pyrimidinylguanidine derivatives.

A simple and straightforward methodology toward the synthesis of novel 4,5-biphenyl-2-pyrimidinylguanidine compounds has been developed by one-pot reaction of biguaninde or dimethyldiguanide with isoflavones. A series of 20 new compounds was reported. All of them were characterized by FT-IR, NMR, and elemental analysis. A typical compound was determined by X-ray diffraction. A variety of substrates can participate in the process with good yields and high purities, making this methodology suitable for library synthesis in drug discovery.

[Synthesis, solubility, lipids-lowering and liver-protection activities of sulfonated formononetin].

A water-soluble compound, sodium formononetin-3'-sulfonate with good lipid-lowering and liver-protection activities was synthesized. It was synthesized by sulfonation reaction, and its structure was characterized by IR, NMR and elemental analyses. The solubility of sodium formononetin-3'-sulfonate in water and n-octanol/water partition coefficient were determined by UV spectrophotometry. The lipid-lowering and liver-protection activities of sodium formononetin-3'-sulfonate were tested by using rat's high fat model induce by feeding with high fat food. The results showed that sodium formononetin-3'-sulfonate not only had favorable water, solubility but also had good lipid-lowering and liver-protection activities.

[Synthesis of biflavones and their interaction with DNA].

To explore new biflavones, 7-hydroxy-8-hydroxymethyl-4'-methoxyisoflavone (1), (5, 7-dihydroxyflavone-8-yl)-(7'-hydroxy-4"-methoxyisoflavone-8'-yl)methane (2), bis(7-hydroxy-4'-methoxyflavone-8-yl) methane (3), bis(3', 5'-diisopropyl-7, 4'-dihydroxy-isoflavone-8-yl)methane (4), and bis(7-hydroxy-isoflavone-8-yl) methane (5) were designed and synthesized from chrysin, formononetin, 7, 4'-dihydroxy-3', 5'-diisopropyl-isoflavone and 7-hydroxy-isoflavone. Their structures were identified with IR, 1H NMR, 13C NMR and elemental analysis. The binding of 1-5 with DNA was studied with fluorescent spectroscopy. Compounds 2-5 showed higher binding affinity with DNA than 1. According to the Stern-Volmer equation, the binding constants of 2, 3 were determined at 35 degrees C and 25 degrees C respectively, they were Kq2 (25 degrees C) = 1.95 x 10(4) Lx mol(-1) and Kq2 (35 degrees C) = 1.67 x 10(4) L x mol(-1); Kq3 (25 degrees C) = 1.89 x 10(4) L x mol(-1) and Kq3 (35 degrees C) = 1.58 x 10(4) L x mol(-1). The quenching mechanism of 2, 3 was suggested as static quenching.

Hexaquacobalt(II) bis(5-hydroxy-7-methoxy-4-oxo-2-phenyl-4H-chromene-6-sulfonate) tetrahydrate.

The title compound, [Co(H(2)O)(6)](C(16)H(11)O(7)S)(2) x 4 H(2)O, with cobalt(II) at the centre of symmetry, exhibits alternating hydrophilic and hydrophobic regions. Hydrophilic regions are generated by O-H...O hydrogen bonds among sulfonate groups, involving solvent water molecules and coordinated water molecules; pi-pi stacking interactions assemble the flavone skeletons into columns which form the hydrophobic regions. A three-dimensional network is built up from an extensive array of hydrogen bonds, pi-pi stacking interactions and electrostatic interactions between the cation and anion. As a salt of the sulfonated derivative of naturally occurring tectochrysin (5-hydroxy-7-methoxyflavone), this compound offers enhanced solubility and potential biological activity over the natural product.

[Synthesis of chrysin derivatives and their interaction with DNA].

Using chrysin as a leading compound, intermediate 5, 7-dihydroxy-6, 8-bis (hydroxymethyl) flavone (1) was synthesized by hydroxymethylation. The intermediate reacted with different alcohols to afford 5, 7-dihydroxy-6, 8-bis ( methoxymethyl) flavone (2), 6, 8-bis (ethoxymethyl) -5, 7dihydroxyflavone (3), 6, 8-bis-(butoxymethyl)-5, 7-dihydroxyflavone (4), 6, 8-bis (pentyloxymethyl) -5,7-dihydroxy flavone (5) and 6, 8-bis-(ethoxymethyl) -5-hydroxy-7-methoxyflavone (6). These compounds were characterized by IR, 1H NMR, 13C NMR and element analysis. The crystal structure of 6 was determined by X-ray crystal diffraction. The interaction of the derivatives with CT-DNA was studied by fluorescent spectroscopy. According to the Stern-Volmer equation, the quenching constants of the compounds 1 - 4 were measured, separately, they were K(q1) = 9.71 x 10(3) L x mol(-1), K(q2) = 2.25 x 10(4) L x mol(-1), K(q3) = 1.03 x 10(4) L x mol(-1) and K(q4) = 7.96 x 10(3) L x mol(-1). Compounds 1-4 showed higher binding affinity with DNA than chrysin did. The results provided the experimental basis for developing a more effective flavonoid and worthing further thoroughly study.

Efficient method for the synthesis of polysubstituted benzenes by one-pot tandem reaction of vinyl malononitriles with nitroolefins.

The one-pot synthesis of polysubstituted benzene derivatives was achieved via vinylogous Michael addition of vinyl malononitriles and nitroolefins as the key step and a sequential tandem reaction. A series of complex aryl compounds such as biphenyls and terphenyls can be obtained with satisfactory yields.

Hydrogen bonding and pi-pi stacking in 6-hydroxybiochanin A monohydrate.

In the lattice of the title compound (systematic name: 5,6,7-trihydroxy-4'-methoxyisoflavone monohydrate), C16H12O6.H2O, the isoflavone molecules are linked into chains through R(4)3(17) motifs composed via O-H...O and C-H...O hydrogen bonds. Centrosymmetric R(4)2(14) motifs assemble the chains into sheets. Hydrogen-bonding and aromatic pi-pi stacking interactions lead to the formation of a three-dimensional network structure.

Hydrogen bonding and pi-pi stacking in methylaminium 4',7-dihydroxyisoflavone-3'-sulfonate dihydrate and hexaaquairon(II) bis(4',7-diethoxyisoflavone-3'-sulfonate) tetrahydrate.

In methylaminium 4',7-dihydroxyisoflavone-3'-sulfonate dihydrate, CH6N+.C15H9O7S-.2H2O, 11 hydrogen bonds exist between the methylaminium cations, the isoflavone-3'-sulfonate anions and the solvent water molecules. In hexaaquairon(II) bis(4',7-diethoxyisoflavone-3'-sulfonate) tetrahydrate, [Fe(H2O)6](C19H17O7S)2.4H2O, 12 hydrogen bonds exist between the centrosymmetric [Fe(H2O)6]2+ cation, the isoflavone-3'-sulfonate anions and the solvent water molecules. Additional pi-pi stacking interactions generate three-dimensional supramolecular structures in both compounds.

[Effects of sodium sulfonate daidzein on stress-induced gastric ulcer and its possible mechanism].

AIM: To investigate the effects of sodium sulfonate daidzein (SSD) on stress-induced gastric ulcer and explore its possible mechanism. METHODS: Using exhausted swimming and counting the number of gastric ulcer to establish the model of stress-induced gastric ulcer. Mouse experience intraperitoneal injection of different doses of SSD and L-NAME, and NDP histochemical method was used to detect the changes of nitric oxide synthase (NOS) positive neurons in stomach. RESULTS: SSD had dose-dependent protective effect on gastric mucosa. L-NAME could prevent stress induced gastric lesion. After combined injection of L-NAME and effective dose of SSD, the protective effect of SSD on gastric mucosa was reinforced. The number of NOS ganglion was constant, and effective dose of SSD had slight effect on NOS-positive neurons in normal mouse while it decreased NOS positive neurons in per area and in per ganglia after stress. CONCLUSION: The increased nitric oxide (NO) leads to gastric ulcer during stress, SSD has protective effect on gastric mucosa and this effect may be mediated by inhibiting NOS and restricting the overproduction of NO during stress.

Hydrogen bonding and pi-pi stacking in hexaaquairon(II) bis(4',7-dimethoxyisoflavone-3'-sulfonate) octahydrate.

In the structure of the title compound, [Fe(H2O)6](C17H13O7S)2.8H2O, 16 hydrogen bonds exist between the centrosymmetric [Fe(H2O)6]2+ cation, the isoflavone-3'-sulfonate anions and the coordinated and solvent water molecules. pi-pi stacking interactions between the isoflavone units, hydrogen bonding and electrostatic interactions result in a three-dimensional supramolecular structure.

Hexaaquanickel(II) bis(4',7-dimethoxyisoflavone-3'-sulfonate) octahydrate.

In the title compound, [Ni(H2O)6](C17H13O7S)2.8H2O, the NiII atom is located on an inversion centre in the space group P2(1)/c. The [Ni(H2O)6]2+, C17H13O7S- and H2O components form many hydrogen bonds and there are pi-pi stacking interactions between the isoflavone units. The hydrogen bonds, pi-pi stacking interactions and electrostatic interactions between the cation and anions link the components into a three-dimensional structure.

Hydrogen bonding and pi-pi stacking in dimethylgenistein.

The title compound, 5-hydroxy-4',7-dimethoxyisoflavone, C17H14O5, is composed of a benzopyranone moiety, a phenyl moiety and two methoxy groups. The benzopyranone ring is not coplanar with the phenyl ring, the dihedral angle between them being 56.28 (3) degrees. The two methoxy groups are nearly coplanar with their corresponding rings, having C-C-O-C torsion angles of 2.9 (2) and 5.9 (2) degrees . The molecules are linked by C-H...O hydrogen bonds into sheets containing classical centrosymmetric R2(2) (8) rings. The sheets are further linked by aromatic pi-pi stacking interactions and C-H...O hydrogen bonds into a supramolecular structure.