Dihydrokawain和Dihydrokawain-5-ol及其立体异构体的全合成

以苯丙醛和手性丙二烯硼酸酯的加成反应及氧化汞催化下甲醇对羟基丙炔酸的加成反应为关键步骤简短完成了Dihydrokawain和Dihydrokawain-5-ol的所有立体异构体的对映选择性全合成.以72%的总产率合成了(+)-Dihy-drokawain,19%的总产率合成了(+)-Dihydrokawain-5-ol.

Effects of Terpinen-4-ol on Four Metabolic Enzymes and Polyphenol Oxidase (PPO) in Mythimna separta Walker

To study insecticidal mechanism of terpinen-4-ol, a main insecticidal composition in the essential oil of Sabina vulgaris, the 5th instar larvae of Mythimna separta, were investigated with terpinen-4-ol by topical application. The activities of phosphatase, glutathione S-transferase （GSTs）, cytochrome P450 （P450）, and polyphenol oxidase （PPO） of tested insects were determined in all poisoning stages, including exciting stage, convulsing stage, paralysis stage, and recover stage. The result showed that the activities of both acid phosphatase （ACP） and alkaline phosphatase （AKP） in treated insects were induced by terpinen-4-ol, but ACP was inhibited in paralysis stage. The activities of GSTs were inhibited in exciting stage, convulsing stage, and paralysis stage, but gradually recovered in recover stage. O-demethylase activity of cytochrome P450 was inhibited by terpinen-4-ol, and the inhibition rate in all poisoning stages were 26.27, 46.03, 80.24, and 90.22%, respectively. PPO activities were strongly inhibited by terpinen-4-ol both in vitro and in vivo. In conclusion, the activities of P450, GSTs, and PPO could have relation with toxicity of terpinen-4-ol against larvae of the Mythimna separta, but recover stage of the poisoning insects might be related to GSTs induced. As a new insecticide or synergist, terpinen- 4-ol has a potential value in field of insecticide resistance management.

A New Flavan-3-ol Glucoside from Daphniphyllum oldhami

A new flavan-3-ol glucoside, (-)-afzelechin-7-O-β-D-glucopyranoside (1), has been isolated from the stem of Daphniphyllum oldhami. The structure of the new compound was elucidated on the basis of detailed spectroscopie analysis and comparison with related compounds.

Inhibition of Na^+,K^+-ATPase in Housefly (Musca domestica L.) by Terpinen-4-ol and Its Ester Derivatives

To reveal the insecticidal mechanism of terpinen-4-ol, the activity of Na＋,K＋-ATPase in insects tested were determined in vivo and in vitro. The results showed that terpinen-4-ol and its ester derivatives had strong contact activity to housefly and the contact toxicities of its derivatives except Z3 were all superior or equivalent to terpinen-4-ol. All the 7 compounds had strong inhibition towards activity of Na＋,K＋-ATPase. With poisoning symptom exacerbating, the inhibition rates were gradually increased. In vitro, the IC50 of terpinen-4-ol, Z1, Z2, Z4, Z5, and Z6 was 155.89, 197.98, 96.02, 121.36, 124.85, and 153.74 μg mL% respectively. There was well correlation between the LDs0 of terpinen-4-ol derivatives to housefly and the IC50 of terpinen-4-ol derivatives to Na＋,K＋-ATPase in housefly. In conclusion, Na＋,K＋-ATPase was likely the target of terpinen-4-ol against insects.

Synthesis and in vitro anti-hepatitis B virus activity of 1H-benzimidazol-5-ol derivatives

A series of 1H-benzimidazol-5-ol derivatives were synthesized and evaluated for their anti-hepatitis B virus(HBV) activity and cytotoxicity in HepG2.2.15 cells.Half of the tested compounds were found to be potent against HBsAg secretion with IC50 values less than 100μmol/L.Compounds 14c,14d,and 14e showed significant inhibitory activity to the viral antigen HBeAg.

Influence of Location of Production, Season and Genotype on Caffeine and Flavan-3-ols in Young Green Tea （Camellia sinensis） Leaves in Kenya

Although tea is grown in agro-ecological regions widely varying in environmental factors affecting yield and quality, planters usually import genetic materials across the different growing regions assuming genotypes with good quality attributes in one location maintain their status in all regions. However, tea quality has not been replicated in new production regions. Black tea quality is influenced by the green leaf quality precursors including caffeine, total polyphenols and individual flavan-3-ols which are precursors of theaflavins and thearubigins, key plain black tea quality parameters. Factors influencing levels of the precursors compounds have not been quantified for popular Kenyan tea cultivars. The influence of geographical production location and seasons on levels and ratios of the quality precursors for 10 black tea popular clones grown in three locations in Kenya under uniform agronomic inputs were monitored. Caffeine varied significantly （P _〈 0.05） with clones and location but not with season. The flavan-3-ols and their ratios all varied （P 〈 0.05） with clones and site but not with season, with significant interactions （P 〈 0.05） between locations and clones, and locations and seasons. These results explain the observed variations in plain black tea quality due to clones and location of production. Thus, farmers in different locations are unlikely to produce black tea of same quality. It is therefore necessary to evaluate new tea genotypes in intended growing areas to establish cultivars suitable for producing high quality plain black teas in the locations. Seasonal variations in plain black tea in Kenya are unlikely to vary significantly due to flavan-3-ols.

Excess Molar Volume and Apparent Molar Volume of Binary Mixtures of 2-Methyl-3-buten-2-ol with 1-Alcohol at 298.15K

Excess molar volumes (V^E_m) of binary mixtures of2-methyl-3-buten-3-ol [CH_3C(OH)(CH_3)CHCG_2] with four 1-alcohols:methanol, ethanol, 1-propanol and l-butanol at 298.15 K andatmospheric pressure are derived from density measurements with avibrating-tube densimeter. All the excess volumes are negative in thesystems over the entire composition range. The results are correlatedwith the Redlich-Kister equation. The effects of chain length ofl-alcohols on V^E_m are discussed. The apparent molar volumes of2-methyl-3-ol and l-alcohols are calculated respectively.

Photoionization and Dissociation Study of 2-Methyl-2-propen-1-ol:Experimental and Theoretical Insights

The photoionization and dissociation of 2-methyl-2-propen-1-ol(MPO)have been investigated by using molecular beam experimental apparatus with tunable vacuum ultraviolet synchrotron radiation in the photon energy region of 8.0-15.5 eV.The photoionization efficiency(PIE)curves for molecule ion and fragment ions:C4H8O^+,C4H7O^+,C3H5O^+,C4H7^+,C4H6^+,C4H5^+,C2H4O^+,C2H3O+,C3H6^+,C3H5^+,C3H3^+,CH3O^+,CHO^+have been measured,and the ionization energy(IE)and the appearance energies(AEs)of the fragment ions have been obtained.The stable species and the first order saddle points have been calculated on the CCSD(T)/cc-pvTZ//B3LYP/6-31+G(d,p)level.With combination of theoretical and experimental results,the dissociative photoionization pathways of 2-methyl-2-propen-1-ol are proposed.Hydrogen migrations within the molecule are the dominant processes in most of the fragmentation pathways of MPO.

Combination of low-concentration of novel phytoestrogen(8,9)-furanyl-pterocarpan-3-ol from Pachyrhizus erosus attenuated tamoxifen-associated growth inhibition on breast cancer T47D cells

Objective:To investigate the estrogenic effect of(8,9)-furanyl-pterocarpan-3-ol(FPC)on growth of human breast cancer T47D cells and the interactions between the FPC and tamoxifen(TAM),on the growth of estrogen receptor-dependent breast cancer T47D cells.Methods:The proliferation effect of FPC were conducted on T47D cells in vitro by MTT test.T47D cells were treated with FPC alone(0.01-200μmol/L)or in combination with TAM 20 nmol/L.Furthermore,the expression of ERαor c-Myc were also determined by immunohistochemistry.Results:The results indicated that administration of an anti-estrogen TAM showed growth inhibitory effect on T47D cells,wheraes co-administered with low concentration(less than 1μmol/L)of FPC attenuated to promote cell proliferation.In contrast,the combination of TAM with higher doses(more than 20μmol/L)of FPC showed growth inhibitory.This result was supported by immunocytochemistry studies that the administration of 20 nmol/L TAM down-regulated ER-αand c-Myc,but the combination of 20 nmol/L TAM and 1μmol/L FPC robustly up-regulated expression of ER-α.Thus,the reduced growth inhibition of TAM 20 nmol/L by FPC 1μmol/L on T47D cells may act via the modulation of ER-α.Conclusions:The findings indicate and suggest that FPC had estrogenic activity at low concentrations and anti-estrogenic effect that are likely to be regulated by c-Myc and estrogen receptors.We also confirm that low concentration of FPC attenuated the growth-inhibitory effects of TAM on mammary tumor prevention.Therefore,the present study suggests that caution is warranted regarding the consumption of dietary FPC by breast cancer patients while on TMA therapy.

Neuropathy and chloracne induced by 3,5,6-trichloropyridin-2-ol sodium:Report of three cases

BACKGROUND Chloracne is a rare skin condition that is caused by systemic exposure to halogenated aromatic compounds.The main characteristic of chloracne is blackhead,and in severe cases,it can be accompanied by systemic symptoms.Sodium 3,5,6-trichloropyridin-2-ol(STCP)is a necessary precursor compound for the production of chlorpyrifos and triclopyr,which are extensively used as a pesticide and herbicide,respectively.STCP is also a chlorophenol that has been associated with chloracne.STCP poisoning could induce mild myelin sheath damage.We herein report three cases with chloracne due to exposure to STCP.CASE SUMMARY Three young men,aged 29,33,and 26 years,respectively,in the same workplace had polymorphic skin lesions,characterized mainly by comedones and cysts,and one of them also had acne like lesions in the genital area.These clinical manifestations appeared when they were exposed to STCP for 3 d,1 wk,and 2 wk,respectively.Among them,polyneuropathy and liver damage occurred.We performed dermoscopy and clinical and laboratory tests on these patients.Additionally,histopathology was used for further diagnosis in the serious patient.These patients were diagnosed with chloracne and separated from STCP.The patients were prescribed oral viaminate capsules,topical adapalene gel,and regular hematologic follow-up for aspartate transaminase and lipids.They are still under follow-up.There was no new lesions and the laboratory tests returned to normal in two patients.Pigmentation and shallow scars remained in the original areas of papules.However,in the most serious patient,new papules still appeared intermittently.All these remind us that the treatment of chloracne caused by STCP is difficult,and we should attach great importance to this new compound related with the neuropathy and chloracne.CONCLUSION STCP is becoming a new chemical product to induce chloracne,which should attract the attention of all medical professionals,especially dermatologists.Due to the lack of knowledge on the new chemical,the diagnosis of chloracne cannot be made in time.Chloracne still deserves our attention.

A FACILE TOTAL SYNTHESIS OF (±)-SELINA-3,11-DIEN-9-OL

A ffcile tatal synthesis of (±)-selina-3. 11-dien-9-ol (1) has been described. The key step is the onepot reductive fragmentation of α,β-unsaturated p-tosylhydrazone and deduction of 9-carbonyl of 5 With sodium borohydride.

Asymmetric synthesis of 3β-acetoxy-17,17-ethylendioxy-15β,16β-methylene-5-androsten-7β-ol

acetoxy-17,17-ethylendioxy-15β,16β-methylene-5-androsten-7β-ol（Ⅰ） was prepared by 3 steps from 3β-acetoxy-15β,16β-methylene-5-androsten-17-one （Ⅱ） with overall yield of 52.7%. Thus, interaction of ethylene glycol and material （Ⅱ） gave 3β-acetoxy- 17,17-ethylendioxy-15β,16β-methylene-5-androsten （Ⅲ） which was subsequently oxidated and stereoselectively reduced to produce compound（Ⅰ）. The normal influencing factors, such as the types of oxidants and reductives, the mole ratio of reactants, the reaction temperature, and the addition ways of reactants, in oxidation and reduction were discussed. The results show that the oxidation rate order is CrO3-C5H5N （1∶1, mole fraction）>CrO3-C5H5N（1∶2）>（C5H5NH）2Cr2O7 in terms of the oxidant, the yield of the oxidation becomes higher with increasing the oxidant stoichiometry and raising the reaction temperature. And the optimum condition is that the reaction temperature is at 30 ℃, and n （Ⅲ）/ n （CrO3-C5H5N（1∶2））=1∶20. The yield of the -7β alcohol order with Li[Al（OC（CH3）3）3H] （e.g.78.6%） is more than that with NaBH4 （e.g.14.5%） in terms of the reductive （agent） and the reduction rate decreases in the course of reaction. The compound （Ⅰ） is characterized by IR and MS.

Crystal Structure of Trans-2-Amino-3-Cyano-4-(3',4'-Methylenedioxyphenyl)-1-Phenyl-2-Cyclopentene-r-1-ol

The crystals of the title compound C19H16N2O3 were synthesized by thereaction of 4, 4-dicyano-1-phenyl-3-(3', 4'-methylenedioxyphenyl)-l-butan withlow-valent titanium reagent. It belongs to the orthorhombic system, space group Pea21with a=11. 547(2), b=13. 168(4), c=10. 645(3) A, V=1618. 4(8) A3, Dc=1.315 g/cm3, Z=4, Mr=320.35. A=0. 71069 A, u(MoKa) =0. 90 cm-1, F(000)=672. The structure was refined to R=0. 036, Rw=0. 044 for 962 observed reflections(I＞3(I) ). X-ray analysis reveals that in the five membered ring the C(11) -C(12)bond is longer than normal double C=C bond while the C(11) -N (1) bond is shorterthan normal C(sp)2-N bond.

Crystal Structure of (1R,4R;1S,4S)2-Amino-3-Cyano-1,4-Diphenyl-2-Cyclopentene-1-ol

The crystal of title compound C18H16N2O was obtained by recrystal-lizing from ethanol solution. It belongs to orthorhombic system, space group Pbca witha=23. 229(2), b=11. 880(3), c=10. 733(3) A, V=2961 (0) A3, Mr=276. 34, Dc=1. 239 g/cm3, Z=8, A(MoKa)=0. 78 cm-1, F(000) =1168. 00. The structurewas refined to R=0. 049 and Rw=0. 046 for 1102 observed reflections (I＞2d(I) ).The bond lengths of C(3) -C(4) and C(3) -N(1) are 1. 349(5) A and 1. 340(6) A,respectively. The bond angles of N (1) -C(3) -C(2), AN (1) -C(3) -C(4), AC(2) -C(3) -C(4) and C(3) -C(4) -C(5) are 121. 1 (4), 128. 4(4), 110. 5(4)and 113. 1 (4), respectively. The dihedral angle between two phenyl rings is 29. 29.

川黄柏中原小檗碱型生物碱及其细胞毒性研究

采用甲醇溶剂对芸香科黄柏属川黄柏的茎进行回流提取,利用硅胶、胺基硅胶和葡聚糖凝胶等多种柱色谱法对提取物化学成分进行研究,通过核磁共振和电喷雾质谱等波谱技术以及与文献报道数据比对,从中分离鉴定了4个原小檗碱型生物碱,分别鉴定为二氢小檗碱(1),hediamine(2),2-methoxy-berbin-10-ol(3),3-methoxy-berbin-10-ol(4).并对化合物1的波谱进行详细归属,对化合物2进行单晶衍射实验,确定其绝对构型.所有化合物均对人肝癌细胞(HepG2)有较强的细胞毒性.

彭泽贝母中二萜类成分

为了研究彭泽贝母的化学成分。利用多种柱色谱方法进行分离纯化,根据光谱数据和理化性质进行结构鉴定。共分离并鉴定了6个对映-贝壳杉类二萜化合物:ent-kauran-15-en-17-ol(I),ent-kauran-15-en-3α,17-diol(II),鄂贝新醇(III),ent-kauran-16α,17-diol(IV),ent-kauran-3α,16α,17-triol(V),ent-16,17-epoxy-kauran-3α-ol(VI)。6个化合物均为首次从彭泽贝母中分得,其中ent-16,17-epoxy-kauran-3α-ol(VI)为新化合物。

安徽贝母中的新二萜成分(英文)

为了研究安徽贝母(FritillariaanhuiensisS.C.ChenetS.E.Yin)的化学成分。将安徽贝母的干燥鳞茎用95%乙醇回流提取后,用硅胶柱色谱进行分离纯化,得到了3个化合物。根据化合物的理化性质和光谱数据进行结构鉴定,分别为12,15-epoxy-8(17),13-labdadien-19-ol(1),ent-3β-acetoxy-kauran-16β,17-diol(2),ent-kaurane-3β,16β,17-triol(3)。化合物1为新的labdane型二萜类化合物,化合物2和3为首次从该植物中得到。

冬虫夏草定殖菌Aspergillus fumigatus中一个新的聚酮类化合物

从冬虫夏草中分离得到一株定殖菌烟曲霉,对其发酵液的乙酸乙酯萃取部位进行化学成分研究,借助正反相硅胶柱色谱及HPLC等方法进行分离纯化,分离得到一个聚酮类新化合物1,利用多种波谱手段(HRESI-MS,1D NMR,2D NMR)确定其结构为为6-methoxy-3-methyl-1H-isochromen-8-ol。化合物1对H1299(人肺癌细胞)、H460(大细胞肺癌细胞)、HGC-27(人胃癌细胞)、A549(人非小细胞肺癌细胞)和mnk-43(人胃癌高分化细胞)五种细胞株均有弱的细胞毒活性。

甜草Oldenlandia cantonensis How的化学成分

研究了民间草药甜草O ldenlandia cantonensisHow的化学成分。从乙醇提取物的乙酸乙酯洗脱部分得到新的五环三萜urs-12-en-29-αoic ac id-3β-ol。该化合物结构通过NMR、IR、MS等波谱数据综合解析确定。研究了urs-12-en-29-αoic ac id-3β-ol对重组人DNA拓扑异构酶Ⅰ、肝癌细胞BEL-7402和胃腺癌细胞MCG-803的抑制作用,效果显著,IC50值分别为12.0×10-6、6.5×10-6、8.0×10-6g/mL。由V(石油醚)∶V(乙酸乙酯)=20∶1洗脱得到的低极性成分进行了气相色谱-质谱分析,共鉴定60个化合物,其中长链脂肪族化合物,如烷烃、饱和及不饱和羧酸(酯)含量较丰富,占36.16%,萜类和甾体类化合物分别占6.42%和9.28%。

西洋参茎叶总皂苷氧化裂解产物中的新侧链环合型达玛烷型三萜

为了研究西洋参茎叶总皂苷氧化碱解产物的组成,对加拿大产西洋参茎叶总皂苷进行氧化碱解后,其产物通过硅胶柱色谱、Sephadex LH-20柱色谱、重结晶等方法进行分离纯化得到2个化合物。根据化合物的理化性质和光谱数据,鉴定其结构为:(12R,20S,24R)-20,24;12,24-diepoxy-24-deisopropyl-dammarane-3β-ol(1)和(20S,24R)-20,24-epoxydammarane-3β,12β,25-triol(2)。化合物1,2均为首次从西洋参茎叶总皂苷碱解产物中分离得到侧链环合的达玛烷型三萜,其中化合物1为新化合物。