Synthesis and Crystal Structure of (Z)-Methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)methyl]phenyl}acrylate

The title compound,(Z)-methyl-3-methoxy-2-{2-[(4-(E-3-p-tolylacryloyl)phenoxy)-methyl]phenyl}acrylate,was synthesized and determined by X-ray single-crystal diffraction.The crystal belongs to the triclinic system,space group P1 with a=8.0157(8),b=12.5748(13),c=13.3768(14)Å,α=64.770(2),β=75.720(2),γ=89.784(2)°,μ=0.085 mm^(-1),Mr=442.49,V=1174.1(2)Å3,Z=2,Dc=1.252 g/cm^(3),F(000)=468,T=294(2)K,R=0.0603 and wR=0.1498 for 2644 observed reflections with I〉2σ(I).X-ray diffraction analysis reveals that the single crystal contains strong non-classical hydrogen bonds.The preliminary bioassay showed that the title compound exhibits inhibitory activity against the Pseudoperoniospora cubensis and Rhizoctonia solani at the test concentration of 200 mg/L.

Synthesis, Crystal Structure and Anti-parasitic Activity of 2-(2-Methoxy-4-nitrophenylcarbamoyl)phenyl 4-Fluorobenzoate

The title compound 2-（2-methoxy-4-nitrophenylcarbamoyl）phenyl-4＇-fluorobenzoate （C21H15FN206, Mr = 410.35）, a fluorine-containing derivative of salicylamide, was conve- niently synthesized through two steps and crystallized in the orthorhombic space group P21/c with a = 7.6453（15）, b = 14.323（3）, c = 17.035（3） A, V= 1865.4（6） A3, Z = 4, Dc = 1.461 Mg/m^3, 2 = 0.71073 A, μ（MoKa） = 0.115 mm-1, F（000） = 848, R = 0.0705 and wR = 0.1834 for 3267 independent refections with 1 〉 2σ（I）. X-ray analysis reveals that the dihedral angles formed between the 2-methoxy-4-nitrobenzene and benzene ring, the benzene and 4-fluorobenzene, and the 2-methoxy-4-nitrobenzene and 4-fluorobenzene ring are 3.2（4）, 69.8（3） and 72.9（2）~, respectively. Bioassay shows that the title compound has anti-parasitic activity against hydatid protoscoleces.

Synthesis and Crystal Structure of 2-[(4-Methoxy- 6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl] Benzoic Acid Methyl Ester

The title compound 2-[(4-methoxy-6-methylthio-2-pyrimidinyl)aminocarbonyl- aminosulfonyl]benzoic acid methyl ester (C15H16N4O6S2, Mr = 412.44) was obtained by the reaction of (4-methoxy-6-methylthio-2-pyrimidinyl)amine with 2-methoxylcarbonylbenzene-sulfonylisocya- nate. The crystal is of monoclinic, space group P21/c with a =11.169(3), b = 9.508(3), c = 17.690(5) ? b = 91.593(5), Z = 4, V = 1877.9(10) 3, Dc = 1.459 g/cm3, F(000) = 856, m(MoKa) = 0.324 mm-1, R = 0.0690 and wR = 0.1368 for 3301 observed reflections (I > 2s(I)). The N(1)H…N(3) and N(2)H…O(4) hydrogen bonds can be observed. In the molecule the phenyl plane(I), pyrimi- din-2-yl-urea bridge plane(Ⅱ) and ester plane(Ⅲ) form three conjugated systems.

4-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzo-furan-5-yl)-N-(pyridin-2-yl)thiazol-2-amine: Chiral Crystal from Achiral Molecule

The title compound 4-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）-N- （pyridin-2-yl） thiazol-2-amine was synthesized by reacting 2-bromo-1-（7-methoxy-2,2-dime- thyl-2,3-dihydrobenzofuran-5-yl）ethanone with 1-（pyridine-2-yl）thiourea, and its crystal was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, chiral space group C2 with a = 18.1328（14）, b = 5.5969（5）, c = 19.2195（15） A, β= 115.5420（10）°, V= 1759.9（2）A3, Z = 4, F（000） = 744, C19H19N3O2S, Mr= 353.43, Dc= 1.334 g/cm3, S = 1.15, μ = 0.201 mm-1, the final R = 0.035 and wR = 0.111 for 2307 observed reflections （I 〉 2σ（I））. The Flack parameter is -0.03（10）. The preliminary bioassay result indicated that the title compound exhibits strong insecticidal activity （93.75% mortality） against Mythimna separate at the concentration of 1.000 g/L.

Synthesis, Crystal Structure and Antitumor Activity of (E)-1-(7-Methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5- yl)-3-(2-methoxyphenyl)-2-(1H-1,2,4-triazol-1-yl)propenol

The title compound, （E）-1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）- 3-（2-methoxyphenyl）-2-（1H-1,2,4-triazol-1-yl）propenol （3a）, was synthesized by the Aldol con- densation reaction of 1-（7-methoxy-2,2-dimethyl-2,3-dihydrobenzofuran-5-yl）-2-（1,2,4-triazol- 1-yl）ethanone with 2-methoxybenzaldehyde and then reduced with NaBH4, and its crystal structure was determined by single-crystal X-ray diffraction： monoclinic system, space group P21 with a = 6.2002（3）, b = 12.8452（7）, c = 13.2257（7） ？, Z = 2, V = 1031.23（9） ？3, Mr = 407.46, Dc = 1.312 Mg/m3, S = 1.054, μ = 0.091 mm-1, F（000） = 432, the final R = 0.0353 and wR = 0.0769 for 3161 observed reflections （I 〉 2σ（I））. X-ray analysis displays that the title compound adopts an E configuration for the C（7）=C（8） double bond and S configuration for the chirality center with the specific rotation of –63.75°. Furthermore, the stability of the crystal was maintained through the intermolecular hydrogen bond O（1）–H？？？N（3）. The antitumor assay exhibits that the title compound 3a （E configuration） has a good antitumor activity against the Hela cell line with the IC50 value of 36.9 μM, which is better than that of 3b （Z configuration）.

Synthesis and Crystal Structure of(E)-Ethyl 2-(4-(2,4-dimethoxybenzylideneamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-3-ylthio)acetate

The crystal structure of the title compound(E)-ethyl 2-(4-(2,4-dimethoxy benzylide-neamino)-5-(3,4,5-trimethoxyphenyl)-4H-1,2,4-triazol-3-ylthio)acetate(4,C_(24)H_(28)N_(4)O_(7)S,Mr=516.17)was synthesized and determined by X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group P2_(1)/n with a=13.162(2),b=8.4506(13),c=22.602(4)Å,β=99.888(3)°,μ=0.183 mm^(-1),V=2476.5(7)Å^(3),Z=4,D_(c)=1.385 g/cm^(3),F(000)=1088,T=110(2)K,R=0.0426 and wR=0.1216 for 3859 observed reflections with I 2σ(Ⅰ).

Argentum 5-Hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate:Synthesis,Crystal Structure and Antitumor Activity

In order to improve the water solubility and bioavailability of 5-hydroxy-7-methoxyflavone,argentum 5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate[Ag4(H2O)6](C(16)H(11)O4SO3)4·H2O(1,C(16)H(11)O4SO3=5-hydroxy-7-methoxy-2-phenyl-4H-chromen-4-one-6-sulfonate)was synthesized by sulfonation reaction.The structure of 1 was characterized by FT-IR,elemental analysis and X-ray single-crystal diffraction.Complex 1 belongs to the triclinic system,space group P1,a=8.077(4),b=12.365(4),c=17.735(7)A,V=1685.0(12)A3,Z=1,μ=1.372 mm^–1,Dc=1.936 g/cm^3,F(000)=984,the final R=0.0819 and wR=0.2332 with I>2σ(I).3D structure of 1 exhibits alternating organic and inorganic regions.O–H×××O hydrogen bonds and Ag–O coordination interactions exist among crystal water,coordinated water and sulfo group,which constructed an organic zone.Flavone skeletons form organic region of 1.Sulfo group is the bridge linking these two regions.The in vitro antitumor activity of 1 against human lymphoma cells U937 and human breast cancer cells MCF-7 were evaluated with CCK-8 assay.The result shows that 1 showed inhibitory activity against tumour cell U937 and MCF-7,and indicated that flavone sulfonate derivatives may be potential leads for further biological screenings and may generate drug-like molecules.

Studies on the Anti-lipid Peroxidative Actions of the Methanolic Extract of the Root of Aegle marmelos and Its Constituents In Vivo and In Vitro

The inhibitory effect of the methanolic extract of the root of Aegle marmelos (MERA) and its constituents on the lipid peroxidation in vivo and in vitro were studied. The results suggested that MERA increased the activities of superoxide dismutase (SOD) and GSH-peroxidase in the liver cytosol of mice, but showed no significant effect on the activity of catalase, and one of its major constituents, 4-methoxy-1-methyl-2-quinolone (MMQ) increased the activity of SOD in liver tissue of mice intoxicated with FeCl2-ascorbic acid (AA)-ADP in vivo. Various constituents isolated from the root of title plant inhibited the lipid peroxidation in rat liver homogenate, which was in vitro induced by FeCl2-ascorbic acid, CCl4-NADPH, or ADP- NADPH. Of the test compounds, MMQ and its derivatives integriquinolone were similar to (-tocopherol in inhibiting MDA production in rat liver microsomes induced by Fe2+-ascorbate, CCl4-NADPH, or ADP-NADPH.

冰糖草化学成分的分离与鉴定

目的研究冰糖草(Scoparia dulcis L.)全草乙醇提取物的正丁醇萃取部位的化学成分。方法运用硅胶、Sephadex LH-20和半制备HPLC等各种方法进行分离纯化,根据理化性质和波谱数据等鉴定化合物结构。结果分离得到16个化合物,分别鉴定为(2S)-7-methoxy-2H-1,4-benzoxazin-3(4H)-one 2-O-β-glucopyranoside(1)、(2R)-7-methoxy-2H-1,4-benzoxazin-3(4H)-one 2-O-β-glucopyranoside(2)、对羟基苯甲酸甲酯(3)、对羟基苯甲醛(4)、2-唑啉酮(5)、对羟基苯乙酮(6)、薏苡素(7)、苯甲酸(8)、对羟基肉桂酸甲酯(9)、黑麦草内酯(10)、异黑麦草内酯(11)、橙酰胺乙酸酯(12)、apigenin 7-O-rutinoside(13)、hispidulin-7-O-rutinoside(14)、isoschaftoside(15)和schaftoside(16)。结论化合物1为新化合物,化合物13~16为首次从冰糖草中分离得到。

A new naphthoquinoneimine derivative from the marine algal-derived endophytic fungus Aspergillus niger EN-13

Cultivation of an endophytic fungus Aspergillus niger EN-13 that was isolated from the inner tissue of the marine brown alga Colpomenia sinuosa resulted in the characterization of a new naphthoquinoneimine derivative, namely, 5,7-dihydroxy-2-[1-（4- methoxy-6-oxo-6H-pyran-2-yl）-2-phenylethylamino]-[ 1,4]naphthoquinone. The structure of the new compound was established on the basis of various NMR spectroscopic analyses including 2D NMR techniques, El-MS, and HR-ESI-MS. This compound displayed moderate antifungal activity.

Nitroxide-Mediated Photo-Controlled/Living Radical Polymerization of Methacrylic Acid

The photo-controlled/living radical polymerization of methacrylic acid (MAA) was performed at room temperature by irradiation with a high-pressure mercury lamp using azo initiators and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl as the mediator in the presence of (4-tert-butylphenyl)diphenylsulfonium triflate (tBuS) as the accelerator. Whereas the bulk polymerization yielded polymers with a bimodal molecular weight distribution in both the absence and presence of tBuS, the solution polymerization in methanol produced unimodal polymers with the molecular weight distribution of 2.0 - 2.3 in the presence of tBuS. The molecular weight distribution of the resulting poly (MAA) decreased with an in- crease in tBuS. The dilution of the monomer concentration also reduced the molecular weight distribution. The use of the initiator with a low 10-h half-life temperature also effectively controlled the molecular weight. The livingness of the polymerization was confirmed by obtaining linear increases in the first-order conversion versus time, the molecular weight versus the conversion, and the molecular weight versus the reciprocal of the initiator concentration.

Elucidation of Acceleration Mechanisms by a Photosensitive Onium Salt for Nitroxide-Mediated Photocontrolled/Living Radical Polymerization

The acceleration mechanisms by a photosensitive onium salt for the nitroxide-mediated photocontrolled/living radical polymerization (photo-NMP) were determined. The photo-NMP of methyl methacrylate was performed by irradiation at room temperature using 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl (MTEMPO) as the mediator and (2RS, 2’RS)-azobis(4-methoxy-2,4-dimethylvaleronitrile) as the initiator. The polymerization was accelerated in the presence of (4-tertbutylphenyl)diphenylsulfonium triflate (tBuS) to produce a polymer with a molecular weight distribution as narrow as the polymerization in its absence. (±)-Camphor-10-sulfonic acid or 2-fluoro-1-methylpyridinium p-toluenesulfonate had no effect on the polymerization speed, suggesting that tBuS did not serve as the photo-acid generator for the photo-NMP. It was found that the acceleration of the polymerization was based on the electron transfer from MTEMPO into tBuS in the excited state to temporarily generate a free radical propagating chain end and an oxoaminium salt (OAS), the one-electron oxidant of MTEMPO. This electron transfer mechanism was verified on the basis of the fact that the photo-NMP in the presence of tBuS was still accelerated by triphenylamine, the electron transfer inhibitor, to partly produce a polymer with an uncontrolled molecular weight. The formation of an uncontrolled molecular weight polymer indicated the generation of a free radical propagating chain end due to the deactivation of the OAS by the triphenylamine. It was deduced that tBuS served as the electron acceptor from MTEMPO in the excited state to temporarily produce a free radical propagating chain end along with OAS, resulting in the acceleration of the polymerization.

青钱柳叶乙酸乙酯部位化学成分的研究

目的研究我国特有植物青钱柳叶中的化学成分。方法利用硅胶色谱法、Sephadex LH-20柱色谱和半制备HPLC等技术手段进行分离纯化,并通过波谱学方法鉴定化合物的结构。结果从青钱柳叶的乙酸乙酯提取物中分离出11个化合物,分别为鉴定为hirsutrin(1)、高山苷B(2)、山柰酚(3)、sterubin(4)、丁香酸(5)、香草酸(6)、2-羟基-5-甲氧基苯甲酸(7)、2-methoxy-4-hydroxycinnamic acid(8)、cis-p-hydroxycinnamic acid(9)、对羟基苯甲酸(10)和对羟基苯甲醛(11)。结论除化合物3和6外其他化合物是首次从该植物中分离得到。

阳桃根中苯醌类化合物的分离鉴定与含量测定

目的：研究阳桃根（ACLR）中苯醌类化学成分的类型及含量测定方法。方法：利用色谱分离法、核磁共振技术对阳桃根药材60％乙醇提取物中的环己烷萃取部位进行分离、鉴定，并应用HPLC法对药材中的苯醌类化学成分进行含量测定。结果：分离得到2个苯醌类化合物：2-methoxy-6-nonyl-cyclohexa．2，5-diene-1，4-dione（MNDD）；2-dodecyl-6-methoxy-cyclohexa-2，5-diene-1，4-dione（DMDD）；MNDD，DMDD分别在0．177～2．657斗g和0．094～1．416μg进样量与峰面积有良好的线性关系；平均加样回收率为98．96％（RSD1．59％），99．55％（RSD0．98％）。结论：首次从植物中分离得到2个苯醌类化合物；HPLC测定方法简便、快速、稳定、准确可靠、重复性好，可用于阳桃根药材中MNDD，DMDD的质量控制。

匙叶八角中的酚性成分

目的研究匙叶八角Illicium spathulatum枝叶的化学成分。方法匙叶八角枝叶的甲醇提取物经醋酸乙酯和正丁醇萃取部分经过反复的硅胶柱色谱、反相柱色谱及Sephadex LH-20凝胶色谱等方法分离,用波谱分析法鉴定化合物结构。结果分离得到了13个酚性化合物,分别鉴定为苏式-(1,2-二羟基丙基)-3,5-二甲氧基苯-4-O-β-D-葡萄糖苷(1)、5,7,3′,4′-tetrahydroxy-2-methoxy-3-flavanone-3-hydrate(2)、4-O-(2-hydroxy-1-hydroxymethylethyl)-dihydroconierylalcohol(3)、2,3-dihydroxy-1-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone(4)、槲皮素(5)、槲皮素-3-O-α-L-吡喃鼠李糖苷(6)、山柰酚(7)、山柰酚-3-O-α-L-吡喃鼠李糖苷(8)、儿茶素(9)、丁香酸-4-O-β-D-吡喃葡萄糖苷(10)、丁香酸甲酯-4-O-β-D-吡喃葡萄糖苷(11)、3,4-二羟基苯甲酸(12)、羟基酪醇(13),同时还分离到大量的莽草酸(14)。结论化合物1是一个新苯丙素葡萄糖苷类化合物,命名为匙叶八角苷。化合物2是首次从植物中分离得到的黄酮醇类物质氧化的水合物,可能是一人工产物,其余化合物均为首次从匙叶八角中分离得到。

New Isoflavonoid Glycosides from the Rhizomes of Iris leptophylla Lingelsh.

Two new isoflavonoid glucosides, 5-hydroxy-6,7-methylenedioxy-isoflavone-4＇-O-D-glucopyranosyl （2→〉l）-L-rhamnoside （irilone-bioside） （compound 1） and 5,4＇-methoxy-6,7-methylenedioxyisoflavone-3＇-O-β-D-glucoside （irisleptophyllidin） （compound 2）, together with five known compounds, nigricanin- 4＇-O-β-D-glucoside （compound 3）, irifloside （compound 4）, irigenin （compound 5）, 5, 3＇, 4＇-trimethoxy-6,7-methylenedioxyisoflavone （compound 6）, and nigricanin （compound 7） were isolated from the alcoholic extract of rhizomes of Iris leptophylla Lingelsh. Their structures were elucidated by spectroscopic methods.