N''''-取代-4-卤代-N-甲基-4′-甲烷磺酰氨基二苯甲酮腙衍生物的合成与生物活性

以对硝基苯甲酰氯、卤代苯、甲烷磺酰氯、水合肼等为原料合成4-卤代-N-甲基-4′-甲烷磺酰氨基二苯甲酮腙,后者与酰氯、醛和酮等反应得到21种新型N′-取代-4-卤代-N-甲基-4′-甲烷磺酰氨基二苯甲酮腙衍生物.所得化合物结构均经1H NMR和MS表征;初步生物活性测试表明这些化合物具有良好的杀虫活性.     

含嘧啶环的新型异噁唑甲酰基脲的合成及生物活性研究

以5-甲基-3-异噁唑甲酰胺、草酰氯和4,6-二取代嘧啶为原料,经两步反应合成了5种N-(4,6-二取代嘧啶)-5-甲基-3-异噁唑甲酰基脲新化合物,其结构经1H NMR、IR和元素分析确证。初步测试了目标化合物对马唐和苘麻等田地杂草的杀除活性,结果表明,部分化合物对马唐有较好的抑制活性。     

无溶剂研磨法合成6-醚基香豆素衍生物及其抑菌活性

[目的]合成6-醚基香豆素衍生物并测试抑菌活性。[方法]邻甲基对苯二酚与乙酰乙酸乙酯经Peachmann缩合得到6-羟基-4,7-二甲基香豆素,随后与取代苄氯无溶剂研磨,合成12个目标化合物4a~4l。[结果]化合物经1H NMR和高分辨质谱鉴定。初步活性试验表明:质量浓度为100 mg/L时,目标化合物对5个靶标真菌有较好的抑菌活性,其中化合物4b、4c和4e对芒果蒂腐病菌的抑制率超过90%。[结论]无溶剂研磨绿色合成了具有较好抑菌活性的6-醚基香豆素衍生物。     

2,3,3a,4,5,6,7,7a-八氢-5-氧代-4,7-桥亚甲基茚的合成

研究了标题化合物的合成新工艺.以双环戊二烯为起始原料,首先与25％的硫酸(n(双环戊二烯)∶n(硫酸)＝1∶1)进行水合反应制得3a,4,5,6,7,7a-六氢-5-羟基-4,7-桥亚甲基茚,收率达82％;其次用5％ Pd/C作为催化剂对3a,4,5,6,7,7a-六氢-5-羟基-4,7-桥亚甲基茚进行加氢反应制得2,3,3a,4,5,6,7-7a-八氢-5羟基-4,7-桥亚甲基茚,收率90％;最后用30％过氧化氢(n(2,3,3a,4,5,6,7-7a-八氢-5羟基-4,7-桥亚甲基茚)∶n(过氧化氢)＝1∶2)氧化加氢产物得到标题化合物,收率84％,反应总收率在58％以上.该过程条件温和,操作简单,污染小,具有工业化应用前景.     

含噻唑啉酮环的氟苯甲酰胺类化合物的合成及抗癌活性研究

以4-氟苯甲酸(1)为原料,通过酯化、肼解制得4-氟苯甲酰肼(2),2再与芳香醛反应得到相应的酰腙(3a-3h),最后以苯和DMF为溶剂,3a-3h与巯基乙酸脱水环化成 2-芳基-3-(4-氟苯甲酰胺基)-4-噻唑啉酮类化合物(4a-4h),并利用IR,1H NMR,13C NMR,ESI-MS和元素分析对4a-4h的结构进行了表征,用MTT法评价了体外对HepG-2, A549-1 和 231-2 3种癌细胞株的体外生长抑制活性。结果表明,4a-4h均具有潜在的体外抑制癌细胞生长活性,其中4b,4f活性最强。     

新型噻唑-腙类化合物的合成及抗肿瘤活性的研究

通过芳基硫脲1a~g与3-氯-2,4-戊二酮2环合得到2-芳氨基-4-甲基-5-乙酰基噻唑3a~g,再与肼基甲酸甲酯4进行缩合反应得到目标产物。以5e为例,分别对反应时间、催化剂种类及物质的量比进行了试验,最佳的缩合反应条件是:反应时间6h,催化剂用浓盐酸,物质的量比1∶1.1,收率70.9%。合成得到7个目标产物2-[1-(2-芳氨基-4-甲基噻唑-5)-乙缩醛]肼基甲酸甲酯5a~g,目标化合物结构经IR、1 H NMR、MS和元素分析确证。采用MTT法对MCF-7和SMMC-7721人肿瘤细胞株进行体外抗肿瘤活性测试,结果发现此类化合物活性较弱,化合物5f有一定的抗肿瘤活性。     

氟吡酰草胺衍生物的合成与生物活性研究

以3-三氟甲基苯酚和4-氯吡啶-2-甲酸为原料,合成了2种新型的具有潜在除草活性的氟吡酰草胺衍生物。其化学结构经~1H NMR得到确证。初步除草活性试验表明:在150 g a.i/hm~2有效剂量下,2个新化合物对双子叶杂草和单子叶杂草具有较好的抑制活性,其中[N-4-甲基苯基-3-(3-三氟甲基苯基)苯氧基]吡啶-2-甲酰胺(化合物3)对牛筋草的茎叶处理抑制率达72.7%。为获得新型高效的除草剂农药提供了参考。     

放线菌SPRI10304次级代谢产物中杀菌活性物质的分离提取及结构鉴定

从苏州地区采集的土壤样品中分离得到能产生杀菌活性物质的菌株SPRI10304.采用硅胶柱层析、薄层层析以及制备高效液相色谱等技术对SPRI10304发酵液中的杀菌活性成分进行分离纯化,得到了1个杀菌活性化合物,经IR、UV、LC-MS、NMR等分析,确定该活性物质的结构为2-乙酰基-3-甲氧基呋喃,俗名异麦芽酚甲醚.该活性物质对黄瓜白粉病有较好的防治效果.     

一种新型含咔唑基的ICT化合物的合成及光谱研究

以芴、咔唑为起始原料,经硝化、还原、烷基化、酰化、缩合六步反应,合成了一种新型ICT化合物9-乙基-3-咔唑亚甲基-芴腙(简称ECzFH)。产物及中间体的结构经IR、1H NMR等测试得到证实,并对其荧光性质进行了初步研究。结果表明,该化合物具有优良的电荷转移效果,且在二甲基亚砜溶剂中发出浅蓝色的荧光(Exmax=295 nm,Emmax1=358 nm,Emmax2=370 nm)。该化合物有望在生物分子探测、光电子集成、光动力学、医学诊断和双光子上转换激射等领域得到应用。     

含1,3,4-■二唑硫醚取代嘧啶乙酰胺的合成及抗真菌活性

[目的]寻找高杀菌活性的1,3,4-■二唑硫醚取代嘧啶乙酰胺类化合物。[方法]以2-甲基4-氨基嘧啶-5-甲酸为原料,通过水解、酯化、肼解、环化、硫醚化和缩合等步骤,合成了10个含1,3,4-■二唑硫醚取代嘧啶乙酰胺化合物。[结果]10个目标化合物通过1H NMR、13C NMR、MS和元素分析进行确证其结构。初步杀菌活性测试表明,20个化合物质量浓度在50 mg/L时,对猕猴桃葡萄座腔菌(Botryosphaeria dothidea)、猕猴桃拟茎点霉菌(Phomopsis sp.)、猕猴桃灰霉菌和蓝莓灰霉菌具有较好的杀菌活性。[结论]1,3,4-■二唑硫醚取代嘧啶乙酰胺化合物具有较好的抗菌活性,在其结构上进一步修饰,期望得到较高活性的化合物。     

海洋微生物源农用抗生活性物质的筛选

对134株海洋微生物(其中49株海洋放线菌、54株海洋细菌、31株海洋真菌)进行农用抗生活性物质筛选,分别测定其发酵上清液和菌丝体浸提液的活体抗植物病源真菌、杀虫、除草活性,发现共有77株菌株具有农用抗生活性,其中7株海洋放线菌的代谢产物的活性较高:3株对植物病原真菌具有较好抑制活性的海洋放线菌代号为Y12–26、P10–16、JWH–09;两株具有较高杀蚜虫活性的海洋放线菌是P10–23、P12–21;两株除草活性较好的海洋放线菌是YY01–17和HH1901–45。     

海洋放线菌Y-0117农用活性代谢产物的研究

在农用抗生素筛选中发现代号为Y-0117的海洋放线茵菌株所产生的代谢产物对植物病原真菌具有良好的抑制作用。对Y-0117发酵液进行萃取、硅胶柱层析、制备薄层色谱、制备HPLC,分离纯化得到两个活性组分0117A和0117B。通过紫外光谱、质谱、核磁共振等手段,确定0117A的分子式为C35H58O8,分子量为604。结构与已知化合物Bafilomycin D相同;0117 B的分子式为C42H60O12．分子量为756,结构与近期发现具有抗癌活性的已知化合物Hygrobafilomycin相同。研究发现0117B对多种植物病原真菌具有良好的抑制活性,对稻瘟病菌的最小抑制浓度为15．63μg·mL^-1。     

海洋来源真菌中二个聚酮类化合物的NMR研究

采用硅胶柱色谱、Sephadex LH-20凝胶柱色谱以及重结晶等方法,从海洋来源真菌Penicillium sacculum发酵液的乙酸乙酯萃取部分中分离得到2个聚酮类化合物：Griseophenone B（Ⅰ）和Griseophenone C（Ⅱ）,通过1DNMR和2DNMR（HSQC,HMBC）等技术确定了化合物的结构。首次报道了化合物Ⅰ的13 CNMR数据以及化合物Ⅱ的核磁共振数据,并利用2DNMR技术对2个化合物的核磁共振信号进行了归属。化合物Ⅱ为首次从该种真菌中分离得到。     

Synthesis,antibacterial and antifungal evaluation of thio- or piperazinyl-substituted 1,4-naphthoquinone derivatives

A series of S-, S,S-, S,O-, N- and N,S-derivatives from 2,3-dichloro-1,4-naphthoquinone compound 1 were synthesized in different reaction media and evaluated for their antibacterial and antifungal activities. The structures of the novel products were characterized by spectroscopic methods, such as microanalysis, ¹H NMR, ¹³C NMR and MS. Among the tested compounds 9, 12 and 18 are the most effective compounds against Candida tenuis as potent antifungal compounds. Compound 9 is also the most effective compound against Staphylococcus aureus as a potent antifungal compound.     

Determination of the Synthetic Cannabinoids JWH-122, JWH-210, UR-144 in Oral Fluid of Consumers by GC-MS and Quantification of Parent Compounds and Metabolites by UHPLC-MS/MS

The consumption of synthetic cannabinoids (SCs) has significantly increased in the last decade and the analysis of SCs and their metabolites in human specimens is gaining interest in clinical and forensic toxicology. A pilot study has been carried out using a combination of an initial last generation gas chromatography-mass spectrometry (GC-MS) screening method for the determination of JWH-122, JWH-210, UR-144) in oral fluid (OF) of consumers and an ultra-high performance liquid chromatography high resolution mass spectrometry (UHPLC-HRMS) confirmatory method for the quantification of the parent compounds and their metabolites in the same biological matrix. OF samples were simply liquid-liquid extracted before injecting in both chromatographic systems. The developed methods have been successfully validated and were linear from limit of quantification (LOQ) to 50 ng/mL OF. Recovery of analytes was always higher than 70% and matrix effect always lower than 15% whereas intra-assay and inter-assay precision and accuracy were always better than 16%. After smoking 1 mg JWH-122 or UR-144 and 3 mg JWH-210, maximum concentration of 4.00–3.14 ng/mL JWH-122, 8.10–7.30 ng/mL JWH-210 ng/mL and 7.40 and 6.81 ng/mL UR-144 were measured by GC-MS and UHPLC-HRMS respectively at 20 min after inhalation. Metabolites of JWH 122 and 210 were quantified in OF by UHPLC-HRMS, while that of UR144 was only detectable in traces. Our results provide for the first time information about disposition of these SCs and their metabolites in consumers OF. Last generation GC-MS has proven useful tool to identify and quantify parent SCs whereas UHPLC-HRMS also confirmed the presence of SCs metabolites in the OF of SCs consumers.     

Methyl Ester ofp-Coumaric Acid: A Phytoalexin-Like Compound from Long English Cucumber Leaves

Methanolic extracts from long English cucumber leaves were fractionated and tested for their fungitoxicity by direct bioassay againstCladosporium cucumerinum on TLC plates. After separation by several preparative TLCs and flash chromatography and purification through reverse-phase HPLC, a crystalline compound possessing antifungal properties was isolated and identified asp-coumaric acid methyl ester. This antifungal compound was found to increase following infection and treatment with Milsana^®, which could explain in part the prophylactic properties of the natural inducer. As such,p-coumaric acid methyl ester is the first identified compound to be associated with phytoalexin-like behavior in cucumber.     

1-甲基-3-(2-甲基环丙基)-1-环丙烯/Cu-β-环糊精（1-MMCPCP/Cu-β-CD）包合物的合成方法

利用β-环糊精成功地制备合成得到粉末状1-甲基-3-(2-甲基环丙基)-1-环丙烯/Cu-β-环糊精(1-MMCPCP/ Cu-β-CD)包合物。经傅里叶转换红外光谱分析（FT-IR）、X射线衍射分析（XRD）、气相色谱-质谱联用分析（GC-MS）、核磁谱（NMR）表征分析证明,得到的1-MMCPCP/Cu-β-CD包合物是1-甲基-3-(2-甲基环丙基)-1-环丙烯（1-MMCPCP）和Cu-β-CD络合物两者分子之间通过一定的相互作用力结合形成的新物相。以失重法测得本实验所得的1-MMCPCP/Cu-β-CD包合物中1-MMCPCP有效含量为2.4%±0.1%。     

新型硫色满酮类化合物的合成及体外抗真菌活性

设计合成9种新型硫色满酮吡唑类化合物,并对其抗真菌活性进行初步评价。首先以取代苯硫酚为起始原料,合成中间体3-次苄基硫色满酮;利用苯甲酰肼与3-次苄基硫色满酮在酸性条件反应生成目标化合物。化合物结构通过核磁共振氢谱、质谱等技术进行确认,抗真菌活性实验表明,9种化合物对部分供试真菌有好的活性。硫色满酮吡唑类化合物在体外的抗真菌活性有待进一步研究。     

Separation and Purification of Gardecin from Gardenia jasminoides Ellis by High-Speed Countercurrent Chromatography

In the present study, a high-speed counter-current chromatography (HSCCC) was investigated for separation and purification of gardecin on a preparative scale. Hexane–ethyl acetate–methanol–water (0.3:1:0.3:1, v/v) was selected as the optimum solvent system to purify gardecin from a fraction obtained from HPD100 column chromatography fractionation of gardenia. After HSCCC isolation, 20.1 mg of gardecin with purity of 97.4% was obtained from 322 g of dry gardenia fruits. Chemical structure identification of this pigment was carried out by MS, ¹H NMR, and ¹³C NMR. Additionally, antioxidant activity of gardecin in comparison with crocin-1 was investigated. The present results demonstrated that gardecin could be efficiently obtained using HSCCC from this herb and this compound features strong antioxidant activity.